Method of coloring hair using cationic dyes

ABSTRACT

The cationic dyes of formula (1) specified in claim 1 are suitable especially for colouring keratin-containing fibres, more especially for colouring hair.

[0001] The present invention relates to a method of colouringkeratin-containing fibres using cationic imidazole dyes, to novelimidazole dyes and to a process for the preparation thereof.

[0002] There is already known from EP-A-714 954 a cationic imidazolazodye that is suitable for colouring hair and is obtained by diazotising4-alkoxyaniline, coupling with imidazole, then alkylating andquaternising, and finally reacting with p-phenylenediamine. That dyedoes not however, meet all the demands made in practice of such directhair dyes, its stability in aqueous solution, in particular, beingunsatisfactory.

[0003] It has now been found that that disadvantage can be overcome byacylating the free aromatic amino group of such dyes or replacing thatgroup with an alkoxy group. As a result the stability is appreciablyimproved and the dyes have adequate storage stability also at relativelyhigh pH values, for example at pH values of from 5 to 10, which is ofdecisive advantage especially for formulations for colouring hair.

[0004] The present invention accordingly relates to a method ofcolouring keratin-containing fibres that comprises treating the fibreswith a dye of formula

[0005] wherein

[0006] Y₁ and Y₂ are each independently of the other hydrogen,unsubstituted or substituted C₁-C₄-alkyl, or halogen,

[0007] R₁ and R₂ are each independently of the other hydrogen orunsubstituted or substituted C₁-C₄alkyl,

[0008] R₃ and R₄ are each independently of the other hydrogen,unsubstituted or substituted C₁-C₄-alkyl, C₁-C₄alkoxy or halogen,

[0009] R₅ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,

[0010] X is C₁-C₁₂alkoxy or a group of formula —N(R₆)—CO—R₇, wherein R₆is hydrogen or C₁-C₄alkyl and R₇ is hydrogen, C₁-C₄alkyl or —NH₂ and

[0011] A⁻ is an anion.

[0012] In accordance with the invention, alkyl radicals are to beunderstood generally as open-chain or branched alkyl radicals, forexample methyl, ethyl, n- and iso-propyl and n-, sec- and tert-butyl.

[0013] The alkyl radicals may be mono- or poly-substituted, for exampleby hydroxy, carboxy, halogen, cyano or C₁-C₄alkoxy.

[0014] The alkoxy radicals may contain from 1 to 12 carbon atoms,preferably from 1 to 4 carbon atoms. They are, for example, methoxy,ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy,n-pentyloxy or n-hexyloxy. The alkoxy groups, too, may be substituted,for example by the radicals mentioned as possible substituents for thealkyl groups, especially by hydroxy or C₁-C₄alkoxy.

[0015] There come into consideration as anion A⁻ both inorganic andorganic anions, for example halide, such as chloride, bromide or iodide,sulfate, hydrogen sulfate, methyl sulfate, boron tetrafluoride,aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, nitrate,benzenesulfonate, formate, acetate, propionate, lactate, and complexanions, such as an anion of a zinc chloride double salt.

[0016] The anion is generally governed by the preparation procedure.Preferably, chlorides, hydrogen sulfates, sulfates, methosulfates,phosphates, formates, lactates or acetates are present.

[0017] Halogen is to be understood as fluorine, bromine or iodine or,especially, chlorine.

[0018] Each of Y₁ and Y₂ is preferably methyl and especially hydrogen.

[0019] Each of R₁ and R₂ is preferably ethyl, hydroxyethyl or methyl.

[0020] R₃ and R₄ are preferably methoxy, methyl, hydrogen or chlorine.

[0021] The preferred meaning of R₅ is hydrogen.

[0022] X is preferably unsubstituted C₁-C₄alkoxy or a radical —NH—CO—R₇,wherein R₇ is especially hydrogen, methyl, ethyl or —NH₂.

[0023] Special preference is given in accordance with the invention tothe use of dyes of formula

[0024] wherein

[0025] R₁ and R₂ are each methyl or ethyl,

[0026] X is unsubstituted C₁-C₄alkoxy or a radical —NH—CO—R₇, wherein R₇is hydrogen, methyl, ethyl or —NH₂ and

[0027] A⁻ is an anion.

[0028] The dyes of formula (2) are novel and the invention relates alsothereto.

[0029] The dyes of formulae (1) and (2) are prepared, for example, byacylating the free amino group in a compound of formula

[0030] wherein Y₁, Y₂, R₁, R₂, R₃, R₄, R₅ and A⁻ are as defined forformula (1), in a manner known per se. This is carried out, for example,by reaction with an appropriate acid, for example formic acid or aceticacid, an anhydride, for example acetic anhydride, or KOCN.

[0031] Compounds of formulae (1) and (2) wherein X is an alkoxy groupare obtained, for example, by reacting a compound of formula

[0032] wherein Y₁, Y₂, R₁, R₂, R₃ and R₄ are as defined for formula (1)and R₈ is C₁-C₄alkyl, with a p-alkoxy-aniline under reaction conditionsknown per se.

[0033] The compounds of formulae (3) and (4) are known or can beobtained in a manner known per se.

[0034] The dyes of formulae (1) and (2) are suitable for colouringkeratin-containing fibres. “Keratin-containing fibres” are to beunderstood as wool, furs, feathers and, especially, human hair.

[0035] A prefered method of colouring keratin-containing fibres of thepresent invention comprises

[0036] a1) treating the fibres with a composition, possessing a pH valueof pH >7, and comprising a developing substance and at least onecoupling substance and an oxidation agent, or

[0037] a2)treating the fibres with a composition, possessing a pH valueof pH <7, comprising a developing substance and at least one couplingsubstance and an oxidation agent, or

[0038] a3) treating the fibres with a dye of formula (1), or with a dyeof formula (4), or with a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance and anoxidation agent, or

[0039] a4) treating the fibres with a dye of formula (1) according toclaim 1, or with a dye of formula (4), or with a composition comprisinga dye of formula (1), and a composition, possessing a pH value of pH <7,and comprising a developing substance and at least one couplingsubstance and an oxidation agent, and

[0040] b) then applying without intermediary rinsing for 5 to 30minutes, and cl)then applying to the treated fibres a composition,possessing a pH value of pH <7, and comprising a developing substanceand at least one coupling substance, or

[0041] c2)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising a developing substance and at leastone coupling substance, or

[0042] c3)then applying to the treated fibres a dye of formula (1)according to claim 1, or a dye of formula (4) or a compositioncomprising a dye of formula (1), and a composition, possessing a pHvalue of pH <7, and comprising a developing substance and at least onecoupling substance, or

[0043] c4)then applying to the treated fibres a dye of formula (1), or adye of formula (4), or a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance, or

[0044] c5)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising a dye of formula (1), or acomposition comprising a dye of formula (1),or

[0045] c6)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising a dye of formula (1), or acomposition comprising a dye of formula (1), with the proviso that leastone dye of formula (1), or a composition comprising a dye of formula(1), applied to the hair.

[0046] One preferred embodiment method of colouring keratin-containingfibres comprises

[0047] a1) treating the fibres with a composition, possessing a pH valueof pH >7, and comprising a developing substance and at least onecoupling substance and an oxidation agent, or

[0048] a2)treating the fibres with a composition, possessing a pH valueof pH <7, comprising a developing substance and at least one couplingsubstance and an oxidation agent, and

[0049] b) then applying without intermediary rinsing for 5 to 30minutes, and

[0050] c3)then applying to the treated fibres a dye of formula (1)according to claim 1, or a dye of formula (4) or a compositioncomprising a dye of formula (1), and a composition, possessing a pHvalue of pH <7, and comprising a developing substance and at least onecoupling substance, or

[0051] c4)then applying to the treated fibres a dye of formula (1), or adye of formula (4), or a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance, or

[0052] c5)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising a dye of formula (1), or acomposition comprising a dye of formula (1),or

[0053] c6)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising a dye of formula (1), or acomposition comprising a dye of formula (1), or in a further embodimentof the invention

[0054] c7)then applying to the treated fibres a dye of formula (1)according to claim 1, or a dye of formula (4) or a compositioncomprising a dye of formula (1), and a composition, possessing a pHvalue of pH <7, and comprising a developing substance and at least onecoupling substance and an oxidation agent, or

[0055] c8)then applying to the treated fibres a dye of formula (1), or adye of formula (4), or a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance and anoxidation agent, or

[0056] c9)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising an oxidation agent and a dye offormula (1), or a composition comprising a dye of formula (1),or

[0057] c10)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising an oxidation agent and a dye offormula (1), or a composition comprising a dye of formula (1),

[0058] with the proviso that least one dye of formula (1), or acomposition comprising a dye of formula (1), applied to the hair.

[0059] One further preferred embodiment method of colouringkeratin-containing fibres comprises

[0060] a3) treating the fibres with a dye of formula (1), or with a dyeof formula (4), or with a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance and anoxidation agent, or

[0061] a4) treating the fibres with a dye of formula (1) according toclaim 1, or with a dye of formula (4), or with a composition comprisinga dye of formula (1), and a composition, possessing a pH value of pH <7,and comprising a developing substance and at least one couplingsubstance and an oxidation agent, and

[0062] b) then applying without intermediary rinsing for 5 to 30minutes, and

[0063] c1)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising a developing substance and at leastone coupling substance, or

[0064] c2)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising a developing substance and at leastone coupling substance, or

[0065] c3)then applying to the treated fibres a dye of formula (1)according to claim 1, or a dye of formula (4) or a compositioncomprising a dye of formula (1), and a composition, possessing a pHvalue of pH <7, and comprising a developing substance and at least onecoupling substance, or

[0066] c4)then applying to the treated fibres a dye of formula (1), or adye of formula (4), or a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance, or

[0067] c5)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising a dye of formula (1), or acomposition comprising a dye of formula (1),or

[0068] c6)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising a dye of formula (1), or acomposition comprising a dye of formula (1), or in a further embodimentof the invention

[0069] c7)then applying to the treated fibres a dye of formula (1)according to claim 1, or a dye of formula (4) or a compositioncomprising a dye of formula (1), and a composition, possessing a pHvalue of pH <7, and comprising a developing substance and at least onecoupling substance and an oxidation agent, or

[0070] c8)then applying to the treated fibres a dye of formula (1), or adye of formula (4), or a composition comprising a dye of formula (1),and a composition, possessing a pH value of pH >7, and comprising adeveloping substance and at least one coupling substance and anoxidation agent, or

[0071] c9)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising an oxidation agent and a dye offormula (1), or a composition comprising a dye of formula (1),or

[0072] c10)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising an oxidation agent and a dye offormula (1), or a composition comprising a dye of formula (1), or

[0073] c11)then applying to the treated fibres a composition, possessinga pH value of pH <7, and comprising a developing substance and at leastone coupling substance, or

[0074] c12)then applying to the treated fibres a composition, possessinga pH value of pH >7, and comprising an oxidation agent and a developingsubstance and at least one coupling substance, or

[0075] with the proviso that least one dye of formula (1), or acomposition comprising a dye of formula (1), applied to the hair.

[0076] In one preferred embodiment of the invention dyes of formula (1)or (4) or further cationic dyes are mixed with the other components ofthe compositions shortly before the applying to the hair.

[0077] In addition, the methods of colouring of the present inventioncan be carried out on hair, with preference being given to locks ofhair, locks of bleached hair, bleached hair, middle blonde hair.

[0078] Further one preffered embodiment of methods of colouring of thepresent invention concerns the colouring by a comb.

[0079] The present invention relates also to compositions comprisingsuch dyes for colouring keratin-containing fibres.

[0080] The compounds of formulae (1) and (2) are present in thecompositions according to the invention preferably in an amount of from0.001% to 5%, especially from 0.01% to 1%, based on the total dyeingcomposition.

[0081] The multiplicity of shades and the colour fastness of the dyes offormulae (1) and (2) used in accordance with the invention can beincreased by combination with other dyes used in the field ofhair-dyeing compositions. They can be combined very readily both withoxidation dyes and with direct dyes, it being possible for the latter tobe of cationic nature or also uncharged. Only in the case of anionicdirect dyes is a certain degree of caution required, since precipitationmay occur in the formulation under certain circumstances.

[0082] In all dyeing compositions, the joint use of a plurality ofdifferent dyeing substances is also possible; similarly possible is thejoint use of a plurality of different oxidation dye precursors from thegroup of the developer and coupler compounds, for example aromaticcompounds having a primary or secondary amino group, nitrogen-containingheterocycles, aromatic hydroxy compounds or amino acids, as described,for example, in German Patent Application 19 717 224.5, especially page3, line 31 to page 5, line 8.

[0083] The dyes of formulae (1) and (2) according to the inventionproduce colour shades in the range from reddish-violet to violet, andthe fastness properties are excellent. Attention is drawn to theproperty thereof that allows hair that is already dark in colour stillto be distinctly altered in shade.

[0084] For colouring hair there are preferably used dyes of formula (1)in admixture with one or more further cationic dyes, especially thosedescribed in particular on pages 11 to 27 of WO 95/01772. Especiallysuitable are dye mixtures comprising a dye of formula (1), and also theyellow dye according to Example 1 and/or the red dye according toExample 4 and/or the orange dye according to Example 46 of WO 95/1772.

[0085] In a further embodiment, for the purpose of further modificationof colour shades the dyeing compositions according to the inventioncomprise, in addition to the dyes of formula (1) according to theinvention, customary direct dyes, for example from the group of thenitroanilines, nitrophenylenediamines, nitroaminophenols,anthraquinones, indophenols, phenazines, phenothiazines, methines or thecompounds known as Arianors, such as, for example, the compounds knownby the international names or trade names HC Yellow 2, HC Yellow 4, HCYellow 6, Basic Yellow 57, Basic Yellow 9, Disperse Orange 3, HC Red 3,HC Red BN, Basic Red 76, Basic Red 2, Basic Violet 14, Basic Blue 3,Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26,HC Blue 2, HC Blue 7, HC Blue 12, Disperse Blue 3, Basic Blue 99, HCViolet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, BasicBrown 16 und Basic Brown 17, and also picramic acid,2-amino-6-chloro-4-nitrophenol,4-amino-2-nitrodiphenylamine-2′-carboxylic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline,4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene hydrochloride and1-methyl-3-nitro4(2′-hydroxyethyl)-aminobenzene.

[0086] Also very suitable for combination with the dyes according to theinvention are cationised nitroaniline and anthraquinone dyes, forexample those described in the following patent specifications: U.S.Pat. No. 5,298,029, especially in column 2, line 33 to column 5, line38; U.S. Pat. No. 5,360,930, especially in column 2, line 38 to column5, line 49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 tocolumn 5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line23 to column 5, line 15; U.S. Pat. No. 5,135,543, especially in column4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2,line 40 to page 3, line 26; U.S. Pat. No. 5,486,629, especially incolumn 2, line 34 to column 5, line 29; and EP-A-758 547, especially onpage 7, line 48 to page 8, line 19.

[0087] Also cationic azo dyes, e.g. according to GB-A-2 319 776, as wellas the oxazine dyes described in DE-A-29 912 327 and mixtures thereofwith the other direct dyes mentioned therein, can likewise readily becombined.

[0088] The compositions of the invention according to this embodimentcontain the dyes preferably in an amount of from 0.01 to 5% by weight,based on the total dyeing composition. In addition, the dyeingcompositions according to the invention may also contain naturallyoccurring dyes, such as, for example, henna red, henna neutral, hennablack, camomile blossom, sandalwood, black tea, Rhamnus frangula bark,sage, campeche wood, madder root, catechu, sedre and alkanet root. Suchcolouring methods are described, for example, in EP-A-404 868,especially page 3, line 55 to page 4, line 9.

[0089] In respect of further customary dye components, reference is madeexpressly to the series “Dermatology”, edited by Ch. Culnan, H. Maibach,Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 7, pages 248-250 (direct dyes), andchapter 8, pages 264 - 267 (oxidation dyes), and to “EuropäischesInventar der Kosmetikrohstoffe”, 1996, published by The EuropeanCommission, obtainable in diskette form from the Bundesverband derdeutschen Industrie-und Handelsunternehmen für Arzneimittel, Reformwarenund Körperpflegemittel e.V., Mannheim.

[0090] It is not necessary for the oxidation dye precursors optionallypresent or for the dyes each to be single compounds, but rather theremay be present in the dyeing compositions according to the invention inaddition, in lesser amounts, further components associated with thepreparation procedures for the individual dyes, provided such componentsdo not have an adverse effect on the dyeing result or do not need to beexcluded for other, for example toxicological, reasons.

[0091] The dyes of formula (1) according to the invention may alsoreadily be used in combination with other dyes and/or adjuvants used inthe colouring of hair, for example with

[0092] oxidising agents to achieve lightened colouration, as describedin WO 97/20545, especially page 9, lines 5 to 9,

[0093] oxidising agents in the form of permanent-wave fixing solution,as described in DE-A-19 713 698, especially page 4, lines 52 to 55, orEP-A-1 062 940, especially page 6, lines 41 to 47, (and in theequivalent WO 99/40895),

[0094] oxidation dyeing compositions, as described in EP-A-850 636,especially page 5, line 41 to page 7, line 52, EP-A-850 637, especiallypage 6, line 50 to page 8, line 44, EP-A-850 638, especially page 7,line 20 to page 9, line 26, and EP-A-852 135, especially page 4, line54to page 6, line 53,

[0095] oxidation dyeing compositions with cationic couplers, asdescribed in WO 99/48856, especially page 9, line 16 to page 13, line 8,and WO 99/48875, especially page 11, line 20 to page 12, line 13,

[0096] oxidation dyes in the presence of oxidoreductase enzyme, asdescribed in WO 99/17730, especially page 4, line 11 to page 13, line28, and WO 99/36034, especially pages 3 to 15,

[0097] autooxidisable oxidation dyes, as described in WO 99/20234,especially page 26, line 16 to page 28, line 15, or

[0098] nitrobenzene derivatives, as described in WO 99/20235, especiallypage 26, line 7 to page 30, line 15,

[0099] polyols or polyethers, as described in EP-A-962 219, especiallypage 27, lines 14 to 38,

[0100] thickening polymers, as described in EP-A-970 684, especiallypage 48, line 16 to page 51, line 4,

[0101] sugar-containing polymers, as described in EP-A-970 687,especially page 28, line 17 to page 29, line 23,

[0102] quaternary ammonium salts, as described in WO 00/10517,especially page 44, line 16 to page 46, line 23,

[0103] anionic surfactants, as described in WO 00/1 0518, especiallypage 45, line 11 to page 48, line 3,

[0104] non-ionic surfactants, as described in WO 00/1 0519, especiallypage 45, line 11 to page 50, line 12, or

[0105] silicones, as described in WO 00/12057, especially page 45, line9 to page 55, line 2.

[0106] The dyeing compositions according to the invention result inintense colourations even at physiologically tolerable temperatures ofless than 45° C. They are accordingly suitable especially for colouringhuman hair. For use on human hair, the dyeing compositions can usuallybe incorporated into an aqueous cosmetic carrier. Suitable aqueouscosmetic carriers include, for example, creams, emulsions, gels and alsosurfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibres.Such forms of use are described in detail in Research Disclosure 42448(August 1999). If necessary, it is also possible to incorporate thedyeing compositions into anhydrous carriers, as described, for example,in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3,line 55. The dyeing compositions according to the invention are alsoexcellently suitable for the colouring method described in DE-A-3 829870 using a colouring comb or a colouring brush.

[0107] The dyeing compositions according to the invention mayfurthermore comprise any active ingredient, additive or adjuvant knownfor such preparations. The dyeing compositions in many cases comprise atleast one surfactant, there being suitable in principle anionic and alsozwitterionic, ampholytic, non-ionic and cationic surfactants. In manycases, however, it has proved advantageous to select the surfactantsfrom anionic, zwitterionic and non-ionic surfactants.

[0108] Anionic surfactants suitable for use in the preparationsaccording to the invention include all anionic surface-active substancesthat are suitable for use on the human body. Such substances arecharacterised by an anionic group that imparts water solubility, forexample a carboxylate, sulfate, sulfonate or phosphate group, and alipophilic alkyl group having approximately from 10 to 22 carbon atoms.In addition, glycol or polyglycol ether groups, ester, ether and amidegroups and also hydroxy groups may be present in the molecule. Thefollowing are examples of suitable anionic surfactants, each in the formof sodium, potassium or ammonium salts or mono-, di- ortri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanolgroup:

[0109] linear fatty acids having from 10 to 22 carbon atoms (soaps),

[0110] ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,in which R is a linear alkyl group having from 10 to 22 carbon atoms andx=0 or from 1 to 16,

[0111] acyl sarcosides having from 10 to 18 carbon atoms in the acylgroup,

[0112] acyl taurides having from 10 to 18 carbon atoms in the acylgroup,

[0113] acyl isothionates having from 10 to 18 carbon atoms in the acylgroup,

[0114] sulfosuccinic mono- and di-alkyl esters having from 8 to 18carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylesters having from 8 to 18 carbon atoms in the alkyl group and from 1 to6 oxyethyl groups,

[0115] linear alkane sulfonates having from 12 to 18 carbon atoms,

[0116] linear α-olefin sulfonates having from 12 to 18 carbon atoms,

[0117] α-sulfo fatty acid methyl esters of fatty acids having from 12 to18 carbon atoms,

[0118] alkyl sulfates and alkyl polyglycol ether sulfates of formulaR′—O(CH₂—CH₂—O)_(x′)—SO₃H, in which R′ is a preferably linear alkylgroup having from 10 to 18 carbon atoms and x′=0 or from 1 to 12,

[0119] mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, especially page 3, lines 40 to 55,

[0120] sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropyleneglycol ethers according to DE-A-3 723 354, especially page 4, lines 42to 62,

[0121] sulfonates of unsaturated fatty acids having from 12 to 24 carbonatoms and from 1 to 6 double bonds according to DE-A-3 926 344,especially page 2, lines 36 to 54,

[0122] esters of tartaric acid and citric acid with alcohols which areaddition products of approximately from 2 to 15 molecules of ethyleneoxide and/or propylene oxide with fatty alcohols having from 8 to 22carbon atoms.

[0123] Preferred anionic surfactants are alkyl sulfates, alkylpolyglycol ether sulfates and ether carboxylic acids having from 10 to18 carbon atoms in the alkyl group and up to 12 glycol ether groups inthe molecule, and also especially salts of saturated and especiallyunsaturated C₈-C₂₂carboxylic acids, such as oleic acid, stearic acid,isostearic acid and palmitic acid.

[0124] Surface-active compounds that carry at least one quaternaryammonium group and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in themolecule are termed zwitterionic surfactants. Zwitterionic surfactantsthat are especially suitable are the so-called betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyl-dimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocamidopropyl betaine.

[0125] Ampholytic surfactants are to be understood as meaningsurface-active compounds that, in addition to a C₈-C₁₈-alkyl or -acylgroup, contain at least one free amino group and at least one —COOH or—SO₃H group in the molecule and are capable of forming internal salts.Examples of suitable ampholytic surfactants include N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkyl-aminopropionate, cocoacylaminoethylaminopropionate andC₁₂-Cleacylsarcosine.

[0126] Non-ionic surfactants contain as the hydrophilic group, forexample, a polyol group, a polyalkylene glycol ether group or acombination of polyol and polyglycol ether groups.

[0127] Such compounds are, for example:

[0128] addition products of from 2 to 30 mol of ethylene oxide and/orfrom 0 to 5 mol of propylene oxide with linear fatty alcohols havingfrom 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbonatoms and with alkylphenols having from 8 to 15 carbon atoms in thealkyl group,

[0129] C₁₂-C₂₂ fatty acid mono- and di-esters of addition products offrom 1 to 30 mol of ethylene oxide with glycerol,

[0130] C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated analoguesthereof,

[0131] addition products of from 5 to 60 mol of ethylene oxide withcastor oil and hydrogenated castor oil,

[0132] addition products of ethylene oxide with sorbitan fatty acidesters,

[0133] addition products of ethylene oxide with fatty acidalkanolamides.

[0134] Examples of cationic surfactants that can be used in thehair-treatment compositions according to the invention are especiallyquaternary ammonium compounds. Preference is given to ammonium halides,such as alkyltrimethylammonium chlorides, dialkyldimethylammoniumchlorides and trialkylmethylammonium chlorides, for examplecetyltrimethylammonium chloride, stearyltrimethylammonium chloride,distearyldimethylammonium chloride, lauryidimethylammonium chloride,lauryldimethylbenzylammonium chloride and tricetylmethylammoniumchloride. Further cationic surfactants that can be used in accordancewith the invention are quaternised protein hydrolysates.

[0135] Also suitable in accordance with the invention are cationicsilicone oils, such as, for example, the commercially available productsQ2-7224 (manufacturer Dow Corning; a stabilisedtrimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising ahydroxylamino-modified silicone, which is also referred to asamodimethicone), SM-2059 (manufacturer General Electric), SLM-55067(manufacturer: Wacker) and also Abilo-Quat 3270 and 3272 (manufacturerTh. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

[0136] Alkylamidoamines, especially fatty acid amidoamines, such as thestearylamidopropyldimethylamine obtainable under the name Tego Amid® 18,are distinguished not only by a good conditioning action but alsoespecially by their good biodegradability Quaternary ester compounds,so-called “esterquats”, such as the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed under thetrade mark Stepantex®, are also very readily biodegradable.

[0137] An example of a quaternary sugar derivative that can be used ascationic surfactant is the commercial product Glucquat® 100, accordingto CTFA nomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride”.

[0138] The alkyl-group-containing compounds used as surfactants may besingle substances, but the use of natural raw materials of vegetable oranimal origin is generally preferred in the preparation of suchsubstances, with the result that the substance mixtures obtained havedifferent alkyl chain lengths according to the particular startingmaterial used.

[0139] The surfactants that are addition products of ethylene and/orpropylene oxide with fatty alcohols or derivatives of such additionproducts may either be products having a “normal” homologue distributionor products having a restricted homologue distribution. “Normal”homologue distribution is to be understood as meaning mixtures ofhomologues obtained in the reaction of fatty alcohol and alkylene oxideusing alkali metals, alkali metal hydroxides or alkali metal alcoholatesas catalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

[0140] Examples of further active ingredients, adjuvants and additivesare as follows:

[0141] non-ionic polymers, for example vinylpyrrolidone/vinyl acrylatecopopylmers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetatecopolymers and polysiloxanes,

[0142] cationic polymers, such as quaternised cellulose ethers,polysiloxanes having quaternary groups, dimethyldiallylammonium chloridepolymers, copolymers of dimethyldiallylammonium chloride and acrylicacid, as available commercially under the name Merquat^(R) 280 and theuse of which in hair colouring is described, for example, in DE-A4421031, especially page 2, lines 20 to 49, or EP-A-953 334, especiallypage 27, line 17 to page 30, line 11, acrylamide/dimethyldiallylammoniumchloride copolymers, diethyl-sulfate-quaternised dimethylaminoethylmethacrylate/vinylpyrrolidone copolymers, vinylpyrrolidonefimidazoliniummethochloride copolymers,

[0143] quaternised polyvinyl alcohol,

[0144] zwitterionic and amphoteric polymers, such as, for example,acrylamidopropyl-trimethylammonium chloride/acrylate copolymers andoctylacrylamide/-methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,

[0145] anionic polymers, such as, for example, polyacrylic acids,crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers,vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobomyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers,

[0146] thickeners, such as agar, guar gum, alginates, xanthan gum, gumarabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulosederivatives, e.g. methyl cellulose, hydroxyalkyl cellulose andcarboxymethyl cellulose, starch fractions and derivatives, such amylose,amylopectin and dextrins, clays, e.g. bentonite or fully synthetichydrocolloids such as, for example, polyvinyl alcohol,

[0147] structuring agents, such as glucose and maleic acid,

[0148] hair-conditioning compounds, such as phospholipids, for examplesoya lecithin, egg lecithin, and cephalins, silicone oils, and alsoconditioning compounds, for example such as those described in DE-A-19729 080, especially page 2, lines 20 to 49, EP-A-834 303, especiallypage 2, line 18 to page 3, line 2, or EP-A-312 343, especially page 2,line 59 to page 3, line 11,

[0149] protein hydrolysates, especially elastin, collagen, keratin, milkprotein, soya protein and wheat protein hydrolysates, condensationproducts thereof with fatty acids and also quaternised proteinhydrolysates,

[0150] perfume oils, dimethyl isosorbitol and cyclodextrins,

[0151] solubilisers, such as ethanol, isopropanol, ethylene glycol,propylene glycol, glycerol and diethylene glycol,

[0152] anti-dandruff active ingredients, such as piroctones, olaminesand zinc Omadine,

[0153] further substances for adjusting the pH value,

[0154] active ingredients such as panthenol, pantothenic acid,allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extractsand vitamins,

[0155] cholesterol,

[0156] light stabilisers and UV absorbers, as described, for example, inEP-A-819 422, especially page 4, lines 34 to 37,

[0157] consistency regulators, such as sugar esters, polyol esters orpolyol alkyl ethers,

[0158] fats and waxes, such as spermaceti, beeswax, montan wax,paraffins, fatty alcohols and fatty acid esters,

[0159] fatty alkanolamides,

[0160] polyethylene glycols and polypropylene glycols having a molecularweight of from 150 to 50 000, for example such as those described inEP-A-801 942, especially page 3, lines 44 to 55,

[0161] complexing agents, such as EDTA, NTA and phosphonic acids,

[0162] swelling and penetration substances, such as polyols and polyolethers, as listed extensively, for example, in EP-A-962 219, especiallypage 27, lines 18 to 38, for example glycerol, propylene glycol,propylene glycol monoethyl ether, butyl glycol, benzyl alcohol,carbonates, hydrogen carbonates, guanidines, ureas and also primary,secondary and tertiary phosphates, imidazoles, tannins, pyrrole,

[0163] opacifiers, such as latex,

[0164] pearlising agents, such as ethylene glycol mono- and di-stearate,

[0165] propellants, such as propane-butane mixtures, N₂O, dimethylether, C₀ ₂ and air, and also

[0166] antioxidants.

[0167] The constituents of the aqueous carrier are used in thepreparation of the dyeing compositions according to the invention in theamounts customary for that purpose; for example emulsifiers are used inconcentrations of from 0.5 to 30% by weight and thickeners inconcentrations of from 0.1 to 25% by weight of the total dyeingcomposition.

[0168] The pH value of the ready-to-use dyeing preparations are usuallyfrom 2 to 11, preferably from 5 to 10.

[0169] To colour keratin-containing fibres,-especially to colour humanhair, the dyeing compositions are usually applied to the hair in anamount of from 50 to 100 g in the form of the aqueous cosmetic carrier,left there for approximately 30 minutes and then rinsed off or washedoff with a commercially available hair shampoo.

[0170] The dyes used according to the invention and the optionally usedoxidation dye precursors may be applied to the keratin-containing fibreseither simultaneously or in succession, the order in which they areapplied being unimportant.

[0171] The dyes used according to the invention and the optionally usedoxidation dye precursors of the compositions according to the inventionmay be stored separately or together, either in a liquid to paste-likepreparation (aqueous or non-aqueous) or in the form of a dry powder.When the components are stored together in a liquid preparation, thepreparation should be substantially anhydrous in order to reducereaction of the components. When they are stored separately, thereactive components are intimately mixed with one another onlyimmediately before use. In the case of dry storage, before use a definedamount of hot (from 50 to 80° C.) water is usually added and ahomogeneous mixure prepared.

[0172] The following Examples serve to illustrate the invention withoutlimiting the invention thereto. Unless specified otherwise, parts andpercentages relate to weight.

EXAMPLE 1 16 g of the Compound of Formula

[0173]

[0174] are introduced into 65 g of acetic anhydride and stirring iscarried out for 2 hours at a bath temperature of approximately 75° C.,after which time all starting material has disappeared. After cooling,filtration is carried out and then washing with acetic anhydride. Inorder to remove the acetic anhydride, the filter cake is suspended in200 ml of isopropanol, and the suspension is stirred for 2 hours andfiltered again and washed with isopropanol. 17.8 g of the compound offormula

[0175] is obtained in very pure form. In aqueous solution, the compounddyes bleached yak hair a brilliant red-tinged violet.

[0176] The acetylation can also be carried out in solvents, for examplein water: 110 g of the above-described starting compound are suspendedin 300 ml of water and, at a temperature of approximately 70° C., atotal of 61.4 g of acetic anhydride (=100% excess) are added over aperiod of one hour. The reaction mixture is cooled with stirring, thenfiltered and washed with water. After drying, 122.5 g of the acetylatedcompound are obtained in which only traces of the starting material arestill present.

EXAMPLE 2 With Stirring, 15 g of the Compound of Formula

[0177]

[0178] are slowly added to 30 g of formic acid (98%) and heating iscarried out for 3 hours at 65° C. 100 ml of isopropanol are addeddropwise to the hot solution, which is then stirred until cold.Filtration followed by thorough washing with isopropanol are carriedout. The moist filter cake is first stirred into 65 ml of methanolbarely at reflux, and then filtration at 45° C. followed by washing withmethanol are carried out. The filter cake is then dissolved hot in 1.5litres of methanol, the solution is clarified and the mother liquor isconcentrated to approximately 85 g using a rotary evaporator, in thecourse of which there is already partial precipitation of the dye. Aftercooling suction filtration is carried out, followed by washing with asmall amount of methanol and drying. Approximately 9 g of the dye offormula

[0179] are obtained. In aqueous solution, the dye colours bleached yakhair a brilliant red-tinged violet.

EXAMPLE 3 10.3 g of the Compound of Formula

[0180]

[0181] are dissolved in 33 ml of 1 N hydrochloric acid in an ice-cooledapparatus. 30 g of ice are added to the reaction solution and then, overa period of half an hour, 2.4 g of potassium cyanate are added inportions. Towards the end a honey-like residue forms, which maysometimes block the stirrer. After standing for from 1 to 2 hours in anice bath, the residue has turned into a brittle mass that can readily becrushed using a glass rod. The suspension, readily stirrable again,still contains significant amounts of starting material and therefore afurther 9 ml of HCl (1 N) and 1.2 g of KOCN are added. The ice bath isthen removed and filtration at room temperature is carried out. Theresidue is suspended in water again and stirred at 75° C. for 2 hours.After cooling, filtration and washing with water are carried out.

[0182] For purification, the residue is dissolved hot in 12 litres ofmethanol and the solution is clarified by way of a preheated pressurisedsuction filter. The filtrate is concentrated to approximately 2 litresusing a rotary evaporator, the dye precipitating in pure form. Followingcooling, filtration and washing with methanol, 24 g of the dye offormula

[0183] are obtained. In aqueous solution, the dye colours bleached yakhair a brilliant violet, the shade of which is slightly less red-tingedthan that of the formyl-substituted dye of Example 2.

EXAMPLE 4

[0184] 13 g of p-anisidine are dissolved at approximately 50° C. in 45 gof dimethylformamide in a suitable stirring apparatus. Then, withstirring, 26.7 g of the compound of formula

[0185] are added in portions and the mixture is stirred for 80 hours ata bath temperature of 90° C. under nitrogen. While still hot, thereaction mixture is diluted with a further 50 g of dimethylformamide,allowed to cool slightly and filtered at approximately 40° C. Thecrystalline filter cake is washed with a further 50 g of DMF inportions, and finally thoroughly suction-filtered dry.

[0186] In order to remove small amounts of starting material that arestill present, the filter cake is suspended in 80 g of water and stirredfor 2 hours at a temperature of from 70 to 75° C. After cooling withstirring, filtration is carried out, followed by washing with a total of50 g of water, in portions, and drying. 22 g of the dye of formula

[0187] are obtained. In aqueous solution, the dye colours bleached yakhair a brilliant red-tinged violet.

EXAMPLE 5

[0188] A 10% solution of a non-ionic surfactant (Plantaren® 2000[Henkel]) is adjusted to pH 9.5 using citric acid. 0.06% of the dye fromExample 1 are dissolved therein. A 1 g strand of undamaged human hair(“Italian white virgin”, Imhair Ltd) is treated for 20 minutes at roomtemperature with 2 g of the dye solution and then rinsed and shampooed.A very attractive violet colouration is obtained, which even afterwashing eight times can still be seen clearly. The fastness to light ofthe colouration is excellent.

EXAMPLE 6

[0189] A 10% solution of a non-ionic surfactant (Plantaren® 2000[Henkel]) is adjusted to pH 5.5 using citric acid. The following dyesare dissolved in 100 g of that solution:

[0190] 0.20 g of the yellow dye according to Example 1 in WO 95/01772

[0191] 0.05 g of the dye according to the invention from Example 4 ofthe present Application.

[0192] A 1 g strand of undamaged human hair (“Italian white virgin”,Imhair Ltd) is treated for 20 minutes at room temperature with 2 g ofthe above dye solution and then rinsed and shampooed. A very attractivecopper colouration having excellent fastness to washing, rubbing andlight is obtained.

EXAMPLE 7

[0193] A 10% solution of a non-ionic surfactant (Plantaren® 2000[Henkel]) is adjusted to pH 5.5 using citric acid. The following dyesare dissolved in 100 g of that solution:

[0194] 0.25 g of the yellow dye according to Example 1 in WO 95/01772

[0195] 0.08 g of the orange dye according to Example 46 in WO 95/01772

[0196] 0.06 g of the dye according to the invention from Example 2 ofthe present Application.

[0197] 0.11 g of the blue dye according to Example 6 in WO 95/01772.

[0198] A strand of bleached human hair is treated for 20 minutes at roomtemperature with double the amount thereof of the above dyeing solution,and is then rinsed and shampooed once. A black colouration having goodfastness to washing and rubbing is obtained.

EXAMPLE 8

[0199] The following cationic emulsion base is prepared:

[0200] 3.8 g of behenic trimonium chloride (Genamin KDM-P [Hoechst])

[0201] 4.0 g of cetyl alcohol (Lanette 16 [Henkel])

[0202] 0.5 g of phenoxyethanol (Uniphen P23 [Induchem])

[0203] 0.1 g of perfume (PO Cinque 226482 [drom])

[0204] water ad 100

[0205] 0.06 g of the dye according to Example 4 of the presentApplication is dissolved in the above base and the pH is adjusted to 6.5using monoethanolamine. A 1 g strand of undamaged medium-brown humanhair (virgin medium-brown hair. lmhair Ltd.) is treated for 20 minutesat room temperature with 2 g of the above dyeing emulsion, and is thenrinsed and shampooed once. The hair acquires a very attractive intenseaubergine shade having excellent fastness properties.

EXAMPLE 9

[0206] A 10% solution of a non-ionic surfactant (Plantaren^(R) 2000[Henkel]) is adjusted to pH 5.5 using citric acid. The following dyesare dissolved in 100 g of that solution:

[0207] 0.06 g of the yellow dye according to Example 1 in WO 95/01772

[0208] 0.09 g of the orange dye according to Example 46 in WO 95/01772

[0209] 0.03 g of the dye according to the invention from Example 4 ofthe present Application

[0210] 0.07 g of the blue dye according to Example 6 in WO 95/01772.

[0211] A strand of bleached human hair and a strand of undamaged whitehuman hair are each treated for 20 minutes at room temperature withdouble the amount thereof of the above dyeing solution, and are thenrinsed and shampooed once. In both cases the result is a dark-browncolouration with a distinct, very attractive violet tinge.

EXAMPLE 10

[0212] The following dyes are dissolved in 100 g of a solution of anon-ionic surfactant as described in Example 5 (pH 9.5):

[0213] 0.14 g of Basic Red 76 (Arianor^(R) Madder Red),

[0214] 0.14 g of the dye according to the invention from Example 4,

[0215] 0.28 g of Basic Blue 99 (Arianor^(R) Steel Blue),

[0216] 0.28 g of HC Yellow 2 and

[0217] 0.14 g of the yellow dye according to Example 1 in WO 95/01772.

[0218] A strand of white, undamaged hair is treated for 20 minutes atroom temperature with the above solution. The result is a light-browncolouration with an attractive copper tinge.

EXAMPLE 11

[0219] The procedure is as in Example 10, except that the dyes specifiedare replaced by

[0220] 0.4 g of the red dye according to Example 3 in WO 95/01772 and

[0221] 0.1 g of the dye according to the invention from Example 4.

[0222] The result on the white hair is a very attractive, intenselyruby-red colouration having excellent fastness properties.

EXAMPLE 12

[0223] Compositions (A) below, in accordance with the invention, areprepared (contents in grams): Composition 1(A) 2(A) 3(A) 4(A) 5(A) 6(A)7(A) 8(A) Para-toluylenediamine 0.25 — — — — — — 0.702,4-Diamino-1-(-(β- — — — — — — — 0.35 hydroxyethyloxy)benzenePara-phenylenediamine — 0.20 — 0.30 1.00 0.70 0.70 — Para-aminophenol0.30 0.50 0.15 — — — — — 5-N-(β-Hydroxyethyl) 0.50 0.80 0.17 — — — — —amino-2-methylphenol 1,3-Dihydroxybenzene — — — — 0.50 0.50 — —5-Amino-methylphenol — — — 0.30 — — — — Cationic dye of example 4 0.150.20 0.05 0.10 0.25 0.10 0.50 0.40 Common dye support (*) (*) (*) (*)(*) (*) (*) (*) (*) Water qs 100 100 100 100 100 100 100 100 (*) Commondye support: Oleyl alcohol polyglycerolated with 4.0 g 2 mol of glycerolOleyl alcohol polyglycerolated with 5.69 g A.M. 4 mol of glycerol,containing 78% active material (A.M.) Oleic acid 3.0 g Oleylaminecontaining 2 mol of ethylene oxide, sold under the trade name EthomeenO12 by the company Akzo Diethylaminopropyllaurylaminosuccinamate, 3.0 gA.M. sodium salt, containing 55% A.M. Oleyl alcohol 5.0 g Oleic aciddiethanolaminde 12.0 g Propylene glycol 3.5 g Ethyl alcohol 7.0 gDipropylene glycol 0.5 g Propylene glycol monomethyl ether 9.0 g Sodiummetabisulphite as an aqueous solution 0.455 g A.M. containing 35% A.M.Ammonium acetate 0.8 g Antioxidant, sequestering agent qs Fragrance,preserving agent qs Aqueous ammonia containing 20% NH₃ 10.0 g

[0224] Compositions 9(A)^(I) to 32 (A)^(I) are identical to composition2(A), and compositions 9(A)^(II) to 32 (A)^(II) are identical tocomposition 4 (A), and compositions 9 (A)^(III) to 32 (A)^(III) areidentical to composition 5(A), and compositions 9 (A)^(IV) to 32(A)^(IV) are identical to composition 6 (A), and compositions 9 (A)^(V)to 32 (A)^(V) are identical to composition 7 (A), with the proviso thatparaphenylenediamine is replaced by a compound C as given below in table1.

[0225] Compositions 34(A)^(I) to 57 (A)^(I) are identical to composition8(A), with the proviso that 2,4-diamino-1-(-(β-hydroxyethyloxy)benzeneis replaced by a compound C as given below in table 1.

[0226] Compositions 59(A)^(I) to 81 (A)^(I) are identical to composition1 (A), and compositions 59(A)^(I′I) to 81 (A)^(I′I) identical tocomposition 8 (A), with the proviso that para-toluylenediamine isreplaced by a compound C as given below in table 1. TABLE 1 CompositionsCompound C  9(A)^(I-V), 34(A)^(I), 59(A)^(I-II) 2-chloro-para-phenylendiamine 10(A)^(I-V), 35(A)^(I), 60(A)^(I-II) 2,3-dimethyl-para-phenylenediamine 11(A)^(I-V), 36(A)^(I), 31(A)^(I-II) 2,6-dimethyl-para-phenylenediamine 12(A)^(I-V), 37(A)^(I), 62(A)^(I-II) 2,6-diethyl-para-phenylenediamine 13(A)^(I-V), 38(A)^(I), 63(A)^(I-II) 2,5-dimethyl-para-phenylenediamine 14(A)^(I-V), 39(A)^(I), 64(A)^(I-II) N,N-dimethyl-para-phenylenediamine 15(A)^(I-V), 40(A)^(I), 65(A)^(I-II) N,N-diethyl-para-phenylenediamine 16(A)^(I-V), 41(A)^(I), 66(A)^(I-II) N,N-dipropyl-para-phenylenediamine 17(A)^(I-V), 42(A)^(I), 66(A)^(I-II)4-amino-N,N-diethyl- 3-methylaniline 18(A)^(I-V), 43(A)^(I),66(A)^(I-II) N,N-bis(.beta.- hydroxyethyl)-para- phenylenediamine19(A)^(I-V), 44(A)^(I), 67(A)^(I-II) 4-amino-N,N-bis(.beta.-hydroxyethyl)-3- methylaniline 20(A)^(I-V), 45(A)^(I), 68(A)^(I-II)4-amino-3-chloro-N,N- bis(.beta.-hydroxyethyl) aniline 21(A)^(I-V),46(A)^(I), 69(A)^(I-II) 2-.beta.-hydroxyethyl- para-phenylenediamine22(A)^(I-V), 47(A)^(I), 70(A)^(I-II) 2-fluoro-para- phenylenediamine23(A)^(I-V), 48(A)^(I), 71(A)^(I-II) 2-isopropyl-para- phenylenediamine24(A)^(I-V), 49(A)^(I), 72(A)^(I-II) N-(.beta.-hydroxypropyl)-para-phenylenediamine 25(A)^(I-V), 50(A)^(I), 74(A)^(I-II)2-hydroxymethyl-para- phenylenediamine 26(A)^(I-V), 51(A)^(I),75(A)^(I-II) N,N-dimethyl-3-methyl- para-phenylenediamine 27(A)^(I-V),52(A)^(I), 76(A)^(I-II) N,N-(ethyl-.beta.- hydroxyethyl)-para-phenylenediamine 28(A)^(I-V), 53(A)^(I), 77(A)^(I-II) N-(.beta.,.gamma.-dihydroxypropyl)-para- phenylenediamine 29(A)^(I-V), 54(A)^(I),78(A)^(I-II) N-(4′-aminophenyl)- para-phenylenediamine 30(A)^(I-V),55(A)^(I), 79(A)^(I-II) N-phenyl-para- phenylenediamine 31(A)^(I-IV),80(A)^(I-II) 2-.beta.-hydroxyethyloxy- para-phenylenediamine32(A)^(I-V), 57(A)^(I), 81(A)^(I-II) 2-.beta.-acetylaminoethyloxy-para-phenylenediamine

[0227] Compositions 100 (A)^(I) to 107(A)^(I) are identical tocomposition 1 (A), and compositions 100(A)^(II) to 107(A)^(II) areidentical to composition 8(A), with the proviso thatpara-toluylenediamine is replaced by a compound C as given below intable 2.

[0228] Compositions 108(A)^(I) to 114(A)^(I) are identical tocomposition 1 (A), and compositions 108(A)^(II) to 114 (A)^(II) areidentical to composition 8 (A), with the proviso thatpara-phenylenediamine is replaced by a compound C as given below intable 2. TABLE 2 Compositions Compound C 100(A)^(I-II), 108(A)^(I-II)N,N′-bis(.beta.-hydroxyethyl)- N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol 101(A)^(I-II), 109(A)^(I-II)N,N′-bis(.beta.-hydroxyethyl)-N, N′-bis(4′-aminophenyl) ethylenediamine103(A)^(I-II), 110(A)^(I-II) N,N′-bis(4-aminophenyl)tetramethylenediamine 104(A)^(II-II), 111(A)^(I-II)N,N′-bis(.beta.-hydroxyethyl)-N 105(A)^(I-II), 112(A)^(I-II)N′-bis(4-aminophenyl) tetramethylenediamine 106(A)^(I-II), 113(A)^(I-II)N,N′-bis(4-methylaminophenyl) tetramethylenediamine 107(A)^(I-II),114(A)^(I-II) N,N′-bis(ethyl)-N,N′-bis (4′-amino-3′-methylphenyl)ethylenediamine

[0229] Compositions 200(A)^(I) to 210(A)^(I) are identical tocomposition 1 (A), and compositions 200(A)^(II) to 210(A)^(II) areidentical to composition 2 (A), and compositions 200(A)^(III) to210(A)^(III) are identical to composition 3 (A), with the proviso thatpara-aminophenol is replaced by a compound C as given below in table 3.TABLE 3 Compositions Compound C 200(A)^(I-III) 4-amino-3-methylphenol203(A)^(I-III) 4-amino-3-fluorophenol 204(A)^(I) _(^(—)) III4-amino-3-hydroxymethylphenol 205(A)^(I-III) 4-amino-2-methylphenol206(A)^(I-III) 4-amino-2-hydroxymethylphenol 207(A)^(I-III)4-amino-2-methoxymethyl-phenol 208(A)^(I-III)4-amino-2-aminomethylphenol 209(A)^(I-III) 4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol 210(A)^(I-III) 4-amino-2-fluoro-phenol

[0230] Compositions 300(A)^(I) to 304(A)^(I) are identical tocomposition 1 (A), and compositions 300(A)^(II) to 304(A)^(II) areidentical to composition 2 (A), and compositions 300(A)^(III) to304(A)^(III) are identical to composition 3 (A), with the proviso thatpara-aminophenol is replaced by a compound C as given below in table 3.TABLE 3 Compositions Compound C 300(A)^(II-I?I) 2-amino-phenol301(A)^(I-III) 2-amino-5-methylphenol 303(A)^(I-III)2-amino-6-methylphenol 304(A)^(I) _(^(—)) III 5-acetamido-2-aminophenol

[0231] Compositions 400(A)^(I) to 404(A)^(I) are identical tocomposition (A), and compositions 400(A)^(II) to 404(A)^(II) areidentical to composition 4(A), and compositions 400(A)^(III) to404(A)^(III) are identical to composition 5(A), and compositions400(A)^(IV) to 404(A)^(IV) are identical to composition 6(A), andcompositions 400(A)^(V) to 404(A)^(V) are identical to composition 7(A),as given above in example 2 with the proviso that para-phenylenediamineis replaced by a compound C as given below in table 4.

[0232] Compositions 405(A)^(I) to 409 (A)^(I) are identical tocomposition 8(A), with the proviso that2,4-diamino-1-(-(β-hydroxyethyloxy)benzene is replaced by a compound Cas given below in table 4.

[0233] Compositions 410(A)^(I) to 414(A)^(I) are identical tocomposition 1(A), and compositions 410(A)^(I′) to 414 (A)^(I′I)identical to composition 8 (A) as given above in example 2 with theproviso that para-toluylenediamine is replaced by a compound C as givenbelow in table 4. TABLE 4 Compositions Compound C 400(A)^(I-V),405(A)^(I), 410(A)^(I-II) 2,4,5,6-tetraaminopyrimidine 401(A)^(I-V),406(A)^(I), 411(A)^(I-II) 4-hydroxy-2,5,6- triaminopyrimidine402(A)^(I-V), 407(A)^(I), 412(A)^(I-II) 4,5-diamino-1-methylpyrazole403(A)^(I-V), 408(A)^(I), 413(A)^(I-II) 3,4-diaminopyrazole404(A)^(I-V), 409(A)^(I), 414(A)^(I-II) 4,5-diamino-1-(4′- chlorobenzyl)pyrazole

[0234] Compositions 500 (A)^(I) to 521 (A)^(I) are identical tocomposition 4(A), 9(A)^(II) to 32 (A)^(II) and 400(A)^(II) to404(A)^(II) with the proviso that 5-amino-2-methylphenol is replaced bya compound C as given below in table 5. TABLE 5 Compositions Compound C500(A)^(I) 5-amino-2-methoxyphenol 501(A)^(I)5-amino-2-(.beta.-hydroxyethyloxy)phenol 502(A)^(I)5-amino-2-methylphenol 503(A)^(I)5-N-(.beta.-hydroxyethyl)amino-2-methylphenol 504(A)^(I)5-N-(.beta.-hydroxyethyl)amino-4-methoxy-2- methylphenol 505(A)^(I)5-amino-4-methoxy-2-methylphenol 506(A)^(I)5-amino-4-chloro-2-methylphenol 507(A)^(I) 5-amino-2,4-dimethoxy-phenol508(A)^(I) 5-(.gamma.-hydroxypropylamino)-2-methylphenol 509(A)^(I)meta-phenylenediamine 510(A)^(I) 3,5-diamino-1-ethyl-2-methoxybenzene511(A)^(I) 3,5-diamino-2-methoxy-1-methylbenzene 512(A)^(I)2,4-diamino-1-ethoxybenzene 513(A)^(I)1,3-bis(2,4-diaminophenoxy)propane 514(A)^(I)bis(2,4-diaminophenoxy)methane 515(A)^(I)1-(.beta.-aminoethyloxy)-2,4-diaminobenzene 516(A)^(I)2-amino-1-(.beta.-hydroxyethyloxy)-4- methylaminobenzene 517(A)^(I)2,4-diamino-1-ethoxy-5-methylbenzene 518(A)^(I)2,4-diamino-5-(.beta.-hydroxyethyloxy)-1- methylbenzene 519(A)^(I)2,4-diamino-1-(.beta.,.gamma.-dihydroxypropyloxy) benzene 520(A)^(I)2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene 521(A)^(I)2-amino4-N-(.beta.-hydroxyethyl)amino-1- methoxybenzene

[0235] Compositions 600 (A)^(I) to 615 (A)^(I) are identical tocomposition 1-8(A), 9(A)^(I-V) to 32 (A)^(I-V), 34(A)^(I) to 57 (A)^(I),59(A)^(I-II) to 81 (A)^(I-II), 100(A)^(I-II) to 107(A)^(I-II),108(A)^(I-II) to 114(A)^(I-III), 200(A)^(I-III) to 210(A)^(I-II),300(A)^(I-III) to 304(A)^(I-III), 400(A)^(I-V) to 404 (A)^(I-V),405(A)^(I) to 409 (A)^(I), 410 (A)^(I) to 414(A)^(I-III) and 500 (A)^(I)to 521 (A)^(I) with the proviso that the common dye support (*) isreplaced by a the common dye support (**) which is identical to thecommon dye support (*) with the proviso that “aqueous ammonia containing20% NH₃”, is replaced by a basifying agent D as given below in table 6.TABLE 6 common dye support (**) basifying agent D 600(A)^(I) pottassiumcarbonate 601(A)^(I) sodium carbonate 602(A)^(I) triethanolamine603(A)^(I) diethanolamnie 604(A)^(I) monoethanolamine 605(A)^(I) sodiumhydroxide 606(A)^(I) potassium hydroxide 607(A)^(I)N,N-dimethyl-N′-ethylenediamine 608(A)^(I) 4-(Ethylamino)-b-butylamine609(A)^(I) N-(n-Propyl)-1,3-propanediamine 610(A)^(I)N,N-diethylenediamine 611(A)^(I) N,N,N′,N′-Tetramethylethylenediamine612(A)^(I) N,N-dimethylhydrazine 613(A)^(I) 2-n-butylaminmoethylamine614(A)^(I) 1,6-diaminohexane 615(A)^(I) 2-amino-2-methyl-1-propanol

EXAMPLE 13

[0236] Compositions B (1 (B), 2(B) and 3(B)) below, in accordance withthe invention, are prepared (contents in grams): 1(B) 2(B) 3(B)1,4-Diaminobenzene 0.40 — — 5-Amino-2-methylphenol 0.45 — —Para-toluylenediamine sulphate — 0.50 0.35 Common dye support (*) as (*)(*) (*) described above in example 12 Demineralized water qs 100 100 100Cationic dye of example 4 4 4 4 Quaternary polyammonia sold 10 10 10under trade name CELQUAT SC-240 by the company National Starch Sawdustqs 100 100 100

[0237] Compositions 4(B)^(I) to 29 (B)^(I) are identical to composition2(B), and compositions 4(B)^(II) to 29 (B)^(II) are identical tocomposition 3 (B), with the proviso that para-toluylenediamine sulphateis replaced by a compound E as given below in table 1.

[0238] Compositions 30 (B)^(I) to 56 (B)^(I) are identical tocomposition 1 (B) with the proviso that 1,4-diaminobenzene is replacedby a compound E as given below in table 1. TABLE 1 Compositions CompoundE  4(B)^(I-II), 30(B)^(I) 2-chloro-para-phenylendiamine  5(B)^(I-II),31(B)^(I) 2,3-dimethyl-para-phenylenediamine  6(B)^(I-II), 32(B)^(I)2,6-dimethyl-para-phenylenediamine  7(B)^(I-II), 33(B)^(I)2,6-diethyl-para-phenylenediamine  8(B)^(I-II), 34(B)^(I)2,5-dimethyl-para-phenylenediamine  9(B)^(I-II), 35(B)^(I)N,N-dimethyl-para-phenylenediamine 10(B)^(I-II), 37(B)^(I)N,N-diethyl-para-phenylenediamine 11(B)^(I-II), 38(B)^(I)N,N-dipropyl-para-phenylenediamine 12(B)^(I-II), 39(B)^(I)4-amino-N,N-diethyl-3-methylaniline 13(B)^(I-II), 40(B)^(I)N,N-bis(.beta.-hydroxyethyl)-para- phenylenediamine 14(B)^(I-II),41(B)^(I) 4-amino-N,N-bis(.beta.-hydroxyethyl)- 3-methylaniline15(B)^(I-II), 42(B)^(I) 4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 16(B)^(I-II), 43(B)^(I) 2-.beta.-hydroxyethyl-para-phenylenediamine 17(B)^(I-II), 44(B)^(I) 2-fluoro-para-phenylenediamine18(B)^(I-II), 45(B)^(I) 2-isopropyl-para-phenylenediamine 19(B)^(I-II),46(B)^(I) N-(.beta.-hydroxypropyl)-para- phenylenediamine 20(B)^(I-II),47(B)^(I) 2-hydroxymethyl-para-phenylenediamine 21(B)^(I-II), 48(B)^(I)N,N-dimethyl-3-methyl-para- phenylenediamine 22(B)^(I-II), 49(B)^(I)N,N-(ethyl-.beta.-hydroxyethyl)- para-phenylenediamine 23(B)^(I-II),50(B)^(I) N-(.beta.,.gamma.-dihydroxypropyl)- para-phenylenediamine24(B)^(I-II), 51(B)^(I) N-(4′-aminophenyl)-para- phenylenediamine25(B)^(I-II), 52(B)^(I) N-phenyl-para-phenylenediamine 26(B)^(I-II),53(B)^(I) 2-.beta.-hydroxyethyloxy-para- phenylenediamine 27(B)^(I-II),54(B)^(I) 2-.beta.-acetylaminoethyloxy- para-phenylenediamine28(B)^(I-II), 55(B)^(I) N-(.beta.-methoxyethyl)-para- phenylenediamine29(B)^(I-II), 56(B)^(I) Para-toluylenediamine

[0239] Compositions 100 (B)^(I) to 109 (B)^(I) are identical tocomposition 1(B), 30(B)^(I) to 56 (B)^(I), with the proviso that5-amino-2-methylphenol is replaced by a compound E as given below intable 2. TABLE 2 Compositions Compound E 100(B)^(I)5-amino-2-methoxyphenol 101(B)^(I)5-amino-2-(.beta.-hydroxyethyloxy)phenol 102(B)^(I)5-amino-2-methylphenol 103(B)^(I)5-N-(.beta.-hydroxyethyl)amino-2-methylphenol 104(B)^(I)5-N-(.beta.-hydroxyethyl)amino-4-methoxy- 2-methylphenol 105(B)^(I)5-amino-4-methoxy-2-methylphenol 106(B)^(I)5-amino-4-chloro-2-methylphenol 107(B)^(I) 5-amino-2,4-dimethoxy-phenol108(B)^(I) 5-(.gamma.-hydroxypropylamino)-2-methylphenol 109(B)^(I)meta-phenylenediamine

[0240] One part by weight of composition B was mixed, at the time ofuse, with 0.1 part by weight of composition (B′) and with one part byweight of a composition (F) comprising a 20-volumes hydrogen peroxidesolution (6% by weight).

[0241] The resulting composition was applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The hair was then rinsed,washed with a standard shampoo and then dried.

[0242] The hair was dyed in a brilliant red-tinged violet shade withvery good endurance properties with respect to subsequent shampooing.

EXAMPLE 14

[0243] The ready-to-use dye compositions below are prepared (contents ingrams): Compositions 1(G) 2(G) 3(G) 4(G) 5(G) 6(G) Para-phenylenediamine0.70 — 0.36 0.55 — 0.283 para-Aminophenol 0.187 — 0.147 —5-N-(β-Hydroxyethyl) 0.21 0.36 — 0.165 0.283 amino-2-methylphenolCationic dye of example 4 0.6 0.065 0.12 0.47 0.051 0.094 Uricase fromArthrobacter 1.5 1.5 1.5 — — — globiformis, at 20 international units(I.U.)/mg, sold by the company Sigma Uric acid 1.5 1.5 1.5 — — — Laccaseissue from Rhus 1.8 1.8 1.8 vernicifere laccase*** at 180 internationalunits (I.U.)/mg sold by the company Sigma Common dye support (*) (*) (*)(*) — — — Common dye support (**) — — — (**) (**) (**) Demineralizedwater qs 100 100 100 — — — Demineralized water qsq — — — 100 100 100 (*)Common dye support: Ethanol 20.0 g Hydroxyethylcellulose sold under thename Natrosol 1.0 g 250 HR ® by the company AqualonPoly(C₈-C₁₀)alkylglucoside as an aqueous solution 8.0 g containing 60%active material (A.M.) buffered with ammonium citrate (0.5%), sold underthe name Oramix CG110 ® by the company SEPPIC Monoethanolamine qs pH = 9(**) Common dye support: Ethanol 20.0 g Poly(C₈-C₁₀)alkylglucoside as anaqueous solution 4.8 g containing 60% active material (A.M.) bufferedwith ammonium citrate (0.5%), sold under the name Oramix CG110 ® by thecompany SEPPIC pH agent Qs pH = 6.5

[0244] Compositions 7(G)^(I) to 32(G)^(I) are identical to composition 1(G), and compositions 7(G)^(II) to 32(G)^(II) are identical tocomposition 3 (G), and compositions 7(G)^(III) to 32(G)^(III) areidentical to composition 4(G), and compositions 9(G)^(IV) to 32(G)^(IV)are identical to composition 6 (G), as given above in example 4 with theproviso that para-phenylenediamine is replaced by a compound H as givenbelow in table 1. TABLE 1 Compositions Compound H 7(G)^(I-IV)para-toluylenediamine 9(G)^(I-IV) 2-chloro-para-phenylendiamine10(G)^(I-IV) 2,3-dimethyl-para-phenylenediamine 11(G)^(I-IV)2,6-dimethyl-para-phenylenediamine 12(G)^(I-IV)2,6-diethyl-para-phenylenediamine 13(G)^(I-IV)2,5-dimethyl-para-phenylenediamine 14(G)^(I-IV)N,N-dimethyl-para-phenylenediamine 15(G)^(I-IV)N,N-diethyl-para-phenylenediamine 16(G)^(I-IV)N,N-dipropyl-para-phenylenediamine 17(G)^(I-IV)4-amino-N,N-diethyl-3-methylaniline 18(G)^(I-IV)N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine 19(G)^(I-IV)4-amino-N,N-bis(.beta.-hydroxyethyl)-3-methylaniline 20(G)^(I-IV)4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 21(G)^(I-IV)2-.beta.-hydroxyethyl-para-phenylenediamine 22(G)^(I-IV)2-fluoro-para-phenylenediamine 23(G)^(I-IV)2-isopropyl-para-phenylenediamine 24(G)^(I-IV)N-(.beta.-hydroxypropyl)-para-phenylenediamine 25(G)^(I-IV)2-hydroxymethyl-para-phenylenediamine 26(G)^(I-IV)N,N-dimethyl-3-methyl-para-phenylenediamine 27(G)^(I-IV)N,N-(ethyl-.beta.-hydroxyethyl)-para-phenylenediamine 28(G)^(I-IV)N-(.beta.,.gamma.-dihydroxypropyl)-para- phenylenediamine 29(G)^(I-IV)N-(4′-aminophenyl)-para-phenylenediamine 30(G)^(I-IV)N-phenyl-para-phenylenediamine 31(G)^(I-IV)2-.beta.-hydroxyethyloxy-para-phenylenediamine 32(G)^(I-IV)2-.beta.-acetylaminoethyloxy-para-phenylenediamine

[0245] Compositions 100(G)^(I) to 110(G)^(I) are identical tocomposition 2 (G), and compositions 200(G)^(II) to 210(G)^(II) areidentical to composition 5 (G), the proviso that para-aminophenol isreplaced by a compound H as given below in table 2. TABLE 2 CompositionsCompound H 200(G)^(I-II) 4-amino-3-methylphenol 203(G)^(I-II)4-amino-3-fluorophenol 204(G)^(I-II) 4-amino-3-hydroxymethylphenol205(G)^(I-II) 4-amino-2-methylphenol 206(G)^(I-II)4-amino-2-hydroxymethylphenol 207(G)^(I-II)4-amino-2-methoxymethyl-phenol 208(G)^(I-II) 4-amino-2-aminomethylphenol209(G)^(I-II) 4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol210(G)^(I-II) 4-amino-2-fluoro-phenol

[0246] Each of the ready-to-use dye compositions are applied for 30minutes. The hair was then rinsed, washed with a standard shampoo andthen dried.

[0247] The locks of hair are dyed in brilliant red-tinged violet shade.

EXAMPLE 15

[0248] The ready-to-use dye compositions below were prepared (contentsin grams): Compositions 1(I) 2(I) 3(I) Behenyl-trimethyl- — 2.0 A.M. —ammonimum cloride Cetyl-trimethylammonimum — — 2.0 A.M. cloride Ethanol10 10 10 Cationic dye of example 1 0.20 0.20 0.102-Amino-2-methyl-1-propanol pH 9 pH 9 pH 9 qs Demineralized water qs 100100 100

[0249] Each of the ready-to-use dye compositions are applied for 30minutes. The hair was then rinsed, washed with a standard shampoo andthen dried.

[0250] The locks of hair were dyed in brilliant red-tinged violet shade.

[0251] Compositions 4(I) to 20(I) are identical to composition 2 (I),the proviso that behenyltrimethylammonimum clodride is replaced by acompound H′ as given below in table 2. TABLE 2 Compositions Compound H′4(I) tetramethylammonium chloride 5(I) diethyl-dimethylammonium chloride6(I) methyl-trimethylammonium chloride 7(I) ethyl-trimethylammoniumchloride 8(I) distearyl-dimethylammonimum cloride 9(I)oleocetyldimetylhydroxyethylammonium chloride 10(I)oleocetylhydroxyethylammonium chloride 11(I)stearamidopropyldimetylammonium chloride sold under the name CERAPHYL 70by the company VAN DYK 12(I)2-hexyldecylamine-1-metyhl-1′-N-(ethylcarbamaic acidhexyldecylamine)-imidazolium methylsulphate sold under the name REWOQUATW 7500 by the company REWO 13(I) propylen-1,3-diammonium chloride 14(I)propylen-1,3-diammonium bromide 15(I) propylen-1,3-diammonium phosphate16(I) propylen-1,3-diammonium sulphate 17(I) propylen-1,3-diammoniumacetat 18(I) propylen-1,3-di-trimetylammonium chloride 19(I)propylen-1,3-di-trimetylammonium sulphate 20(I)propylen-1,3-di-trimetylammonium acetate

[0252] Compositions 1(I)′ to 20 (I)′ are identical to compositions 1(I)to 20(I), with the proviso that ethanol is replaced by isopropanol.Compositions 1(I)″ to 15(I)″ are identical to compositions 1(I) to 20(I)and 1(I)′ to 20 (I)′, with the proviso that 2-amino-2-methyl-1-propanolis replaced by a basifying agent D′. Compositions 1(I)″ to 15(I)″basifying agent D′ 1(I)^(II) pottassium carbonate 2(I)^(II) sodiumcarbonate 3(I)^(II) triethanolamine 4(I)^(II) diethanolamnie 5(I)^(II)monoethanolamine 6(I)^(II) sodium hydroxide 7(I)^(II) potassiumhydroxide 8(I)^(II) N,N-dimethyl-N′-ethylenediamine 9(I)^(II)4-(Ethylamino)-b-butylamine 10(I)^(II) N-(n-Propyl)-1,3-propanediamine11(I)^(II) N,N-diethylenediamine 12(I)^(II)N,N,N′,N′-Tetramethylethylenediamine 13(I)^(II) N,N-dimethylhydrazine14(I)^(II) 2-n-butylaminmoethylamine 15(I)^(II) 1,6-diaminohexane

EXAMPLE 16

[0253] The ready-to-use dye compositions below are prepared (contents ingrams): Composition 1(L) 2(L) 2-Amino-5-hydroxy- 0.35 — nitrobenzene2-N-(β-Hydroxyethyl) — 0.25 amino-5-aminonitrobenzene Cationic dye*0.065 0.04 Common dye support (*) (*) (*) Demineralized water qs 100 100(*) Common dye support: Ethanol 20.0 g Nonylphenoloxyethylen with 9 moloxyethylen  8.0 g sold under the name IGEPAL NR 9 Or by the companyRHODIA CHEMIE 2-Amino-2-methyl-1-propanol qs. pH = 9.5 • *Cationic dyeis mixed with the other components of the oxidative dye compositionshortly before the applying to the hair. • *Cationic dye is a singlecationic dye or composition of cationic dyes as given above compositions(V^(I)) = compositions (V^(I))′ = composition 1 L + composition 2 L +*Cationic dye *cationic dye *cationic dye Cationic dye of example 110(V^(I)) 10(V^(I))′ Cationic dye of example 2 11(V^(I)) 11(V^(I))′Cationic dye of example 3 12(V^(I)) 12(V^(I))′ Cationic dye of example 413(V^(I)) 13(V^(I))′ compositions (V^(I)) = composition 1 L + *cationicdye + **dye (*cationic dye/**dye in a ratio of 1:1) cationic dyecationic dye cationic dye cationic dye **Dye of example 1 of example 2of example 3 of example 4 HC Yellow 2 14(V^(I)) 15(V^(I)) 16(V^(I))17(V^(I)) HC Yellow 4 18(V^(I)) 19(V^(I)) 20(V^(I)) 21(V^(I)) HC Yellow6 22(V^(I)) 23(V^(I)) 24(V^(I)) 25(V^(I)) Basic Yellow 57 26(V^(I))27(V^(I)) 28(V^(I)) 29(V^(I)) Basic Yellow 9 30(V^(I)) 31(V^(I))32(V^(I)) 33(V^(I)) Disperse Orange 3 34(V^(I)) 35(V^(I)) 36(V^(I))37(V^(I)) HC Red 3 38(V^(I)) 39(V^(I)) 40(V^(I)) 41(V^(I)) HC Red BN42(V^(I)) 43(V^(I)) 44(V^(I)) 45(V^(I)) Basic Red 76 46(V^(I)) 47(V^(I))48(V^(I)) 49(V^(I)) Basic Red 2 50(V^(I)) 51(V^(I)) 52(V^(I)) 53(V^(I))Basic Violet 14 54(V^(I)) 55(V^(I)) 56(V^(I)) 57(V^(I)) Basic Blue 358(V^(I)) 59(V^(I)) 60(V^(I)) 61(V^(I)) Basic Blue 6 62(V^(I)) 63(V^(I))64(V^(I)) 65(V^(I)) Basic Blue 7 66(V^(I)) 67(V^(I)) 68(V^(I)) 69(V^(I))Basic Blue 9 70(V^(I)) 71(V^(I)) 72(V^(I)) 73(V^(I)) Basic Blue 1274(V^(I)) 75(V^(I)) 76(V^(I)) 77(V^(I)) Basic Blue 26 78(V^(I))79(V^(I)) 80(V^(I)) 81(V^(I)) HC Blue 2 82(V^(I)) 83(V^(I)) 84(V^(I))85(V^(I)) HC Blue 7 86(V^(I)) 87(V^(I)) 88(V^(I)) 89(V^(I)) HC Blue 1290(V^(I)) 91(V^(I)) 92(V^(I)) 93(V^(I)) Disperse Blue 3 94(V^(I))95(V^(I)) 96(V^(I)) 97(V^(I)) HC Violet 1 98(V^(I)) 99(V^(I)) 100(V^(I))101(V^(I)) Disperse Violet 1 102(V^(I)) 103(V^(I)) 104(V^(I)) 105(V^(I))Disperse Black 9 106(V^(I)) 107(V^(I)) 108(V^(I)) 109(V^(I)) Basic Brown16 110(V^(I)) 111(V^(I)) 112(V^(I)) 113(V^(I)) Basic Brown 17 114(V^(I))115(V^(I)) 116(V^(I)) 117(V^(I)) 2-amino-6-chloro-4-nitrophenol118(V^(I)) 119(V^(I)) 120(V^(I)) 121(V^(I))4-amino-2-nitrodiphenylamine-2′-carboxylic acid 122(V^(I)) 123(V^(I))124(V^(I)) 125(V^(I)) 6-nitro-1,2,3,4-tetrahydroquinoxaline 126(V^(I))127(V^(I)) 128(V^(I)) 129(V^(I))4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene 130(V^(I))131(V^(I)) 132(V^(I)) 133(V^(I)) hydrochloride1-methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene 135(V^(I)) 136(V^(I))137(V^(I)) 138(V^(I)) compositions (V^(I)) = composition 1 L + *cationicdye + ***dyes (*cationic dye/***dye in a ratio of 1:1) cationic dyecationic dye cationic dye cationic dye Dyes*** of example 1 of example 2of example 3 of example 4 HC Yellow 2, HC Yellow 4 139(V^(I)) 140(V^(I))141(V^(I)) 142(V^(I)) Basic Red 76, HC Red BN, 143(V^(I)) 144(V^(I))145(V^(I)) 146(V^(I)) HC Red BN, Basic Violet 14 147(V^(I)) 148(V^(I))149(V^(I)) 150(V^(I)) Basic Blue 12, Basic Blue 6 151(V^(I)) 152(V^(I))153(V^(I)) 154(V^(I))4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene 155(V^(I))156(V^(I)) 157(V^(I)) 158(V^(I)) hydrochloride,6-nitro-1,2,3,4-tetrahydroquinoxaline Basic Brown 16, Disperse Black 9159(V^(I)) 160(V^(I)) 162(V^(I)) 163(V^(I)) compositions (V^(I)) =composition 1 L + *cationic dye + ****dyes (*cationic dye/****dye in aratio of 1:1) cationic dye cationic dye cationic dye cationic dyeDyes**** of example 1 of example 2 of example 3 of example 4 HC Yellow2, HC Yellow 4, Basic Red 2 164(V^(I)) 165(V^(I)) 166(V^(I)) 167(V^(I))Basic Red 76, HC Red BN, Basic Red 2 168(V^(I)) 169(V^(I)) 170(V^(I))171(V^(I)) HC Red BN, Basic Violet 14, Disperse Violet 1 172(V^(I))173(V^(I)) 174(V^(I)) 175(V^(I)) Basic Blue 12, Basic Blue 6, DisperseViolet 1 176(V^(I)) 177(V^(I)) 178(V^(I)) 179(V^(I))2-amino-6-chloro-4-nitrophenol, 6-nitro- 180(V^(I)) 181(V^(I))182(V^(I)) 183(V^(I)) 1,2,3,4-tetrahydroquinoxaline, Basic Brown 17Basic Brown 16, Disperse Black 9, Basic Brown 17 184(V^(I)) 185(V^(I))186(V^(I)) 187(V^(I)) compositions (V^(I)) = composition 1 L + *cationicdye + ******dyes (*cationic dye/*****dye in a ratio of 1:1) cationic dyecationic dye cationic dye cationic dye Dyes***** of example 1 of example2 of example 3 of example 4 HC Yellow 2, Basic Red 76, Basic Red 2,Disperse Orange 3 188(V^(I)) 189(V^(I)) 190(V^(I)) 191(V^(I)) Basic Red76, HC Red BN, Basic Red 2, Basic Violet 14 192(V^(I)) 193(V^(I))194(V^(I)) 195(V^(I)) HC Red BN, Basic Violet 14, Disperse Violet 1, HCRed 3 196(V^(I)) 197(V^(I)) 197(V^(I)) 198(V^(I)) Basic Blue 12, BasicBlue 6, Disperse Violet 1, Basic Blue 9 199(V^(I)) 200(V^(I)) 201(V^(I))202(V^(I)) 2-amino-6-chloro-4-nitrophenol, 6-nitro- 203(V^(I))204(V^(I)) 205(V^(I)) 206(V^(I)) 1,2,3,4-tetrahydroquinoxaline, BasicBrown 17, HC Red BN Basic Brown 16, Disperse Black 9, Basic Brown 17,Basic Red 76 207(V^(I)) 208(V^(I)) 209(V^(I)) 210(V^(I))

[0254] Each of the ready-to-use dye compositions are applied for 30minutes. The hair is then rinsed, washed with a standard shampoo andthen dried.

[0255] The locks of hair are dyed in brilliant shades.

EXAMPLE 17

[0256] The powdery dye composition 1 (M) is prepared as given below:Composition 1(M) (%-by weight) Hydroxypropyl-Guar-triamoniumchloride20.00 Cycloocatamylose 4.00 PEG-150/PPG 301 16.00 Polyethylenglycol (MW10000) 48.20 Com proteine hydrolysate 5.00 Honey dried extract 2.00Potassium sorbat 2.00 Cationic dye of formula (I) of example 1 0.2

[0257] An oxidative dye powder for hair, composition 2(M), is preparedas given below: Composition 2(M) (%-by weight) p-Toluylendiaminsulphate3.0 Resorcine 1.0 3-Aminophenolsulphate 0.3 m-Phenylendiaminehydrochloride 0.2 Silicon dioxide 0.5 sodium lauryl sulphate 0.2 sodiumalginate 3.5 sodium meta silica 0.4 potassium sulphite 0.1

[0258] Compositions 2(M)′ to 33 (M)′ are identical to composition 2(M),with the proviso that resorcine is replaced by a compound M′ as given inthe table below.

[0259] Compositions 2(M)″ to 33 (M)″ are identical to composition 2(M),with the proviso that m-phenylendiamine hydrochloride is replaced by acompound M′ as given in the table below.

[0260] Compositions 2(M)′″ to 33 (M)′″ are identical to composition2(M), with the proviso that 3-aminophenolsulphate is replaced by acompound M′ as given in the table below.

[0261] Compositions 2(M)^(IV) to 33 (M)^(IV) are identical tocomposition 2(M), with the proviso that 3-aminophenolsulphate,m-phenylendiamine hydrochloride and resorcine is replaced by 1.5%-byweight of a compound M′ as given in the table below. Composition 2(M)compound M′ 1(M)^(I-IV) 2-methylresorcine 2(M)^(I-IV) 4-chloroesorcine3(M)^(I-IV) 2-amino-4-chlorophenol 4(M)^(I-IV) 4-(N-methyl)aminophenol5(M)^(I-IV) 2-aminophenol 6(M)^(I-IV) 3-aminophenol 7(M)^(I-IV)1-methyl-2-hydroxy-4-aminobenzene 8(M)^(I-IV) 3-N,N-dimethylaminophenol9(M)^(I-IV) 4-amino-3-methylphenol 10(M)^(I-IV) 5-amino-2-methylphenol11(M)^(I-IV) 6-amino-3-methylphenol 12(M)^(I-IV)3-amino-2-methylamino-6-methoxypyridine 13(M)^(I-IV)2-amino-3-hydroxypyridine 14(M)^(I-IV) 4-aminodiphenylamine 15(M)^(I-IV)4,4′-diaminodophenylamine 16(M)^(I-IV) 2-dimethylamino-5-aminopyridine17(M)^(I-IV) 2,6-diaminopyridine 18(M)^(I-IV) 1,3-diaminobenzol19(M)^(I-IV) 1-amino-3-(2′-hydroxyethylamino)benzene 20(M)^(I-IV)1-amino-3-[bis(2′-hydroxyethyl)amino]benzene 21(M)^(I-IV)1,3-diaminotoluene 22(M)^(I-IV) α-naphthol 23(M)^(I-IV)1,4-diamino-2-chlorobenzene 24(M)^(I-IV) 4,6-dichlororesorcine25(M)^(I-IV) 4-hydroxy-1,2-methylendioxybenzene 26(M)^(I-IV)1,5-dihydroxynaphthaline 27(M)^(I-IV) 1,7-dihydroxynaphthaline28(M)^(I-IV) 2,7-dihydroxynaphthaline 29(M)^(I-IV) 1-hydroxynaphthaline30(M)^(I-IV) 4-hydroxy-1,2-methylenedioxybenzene 31(M)^(I-IV)2,4-diamino-3-chlorophenol 32(M)^(I-IV)1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzene 33(M)^(I-IV)2,4-diamino-3-chlorophenol and 1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzene

[0262] Dying Process

[0263] a) Bleached human hair is pretreated with a common permanent waveon the basis of thioglycolic acid at a pH value in the range of 9.0 to9.5 and then rinsed with water. Afterwards, the hair is treated with thepowdery dye composition 1 (M) or 1 (M)^(I-V) to 33(M)^(I-IV) and 40 mlstabilized peroxide solution (6% by weight).

[0264] The powdery dye composition is applied for 5 to 10 minutes andthen rinsed with water and in following, dried.

[0265] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing.

[0266] b) A fixing solution, composition 3(M), is prepared as givenbelow: fixing solution, composition 3(M) (%-by weight) Peroxide solution4.8 PPG30/PEG150 1.0 Cocosamineoxide 0.6 Coco fatty acid/collagenhydrolysate, potassium salt 0.5 Polyquaternium-35 0.5 Sodiumphosphate0.4 Phosphore acid 0.3 Citronic acid 0.3 Demineralized Water qs 100

[0267] 10 g of composition 2(M) is mixed with 80 ml of composition 3(M).The resulting mixture is applied on bleached human hair, which waspretreated with a common permanent wave on the basis of thioglycolicacid at a pH value in the range of 9.0 to 9.5 for 10 minutes. Afterwarsthe hair is rinsed and dried.

[0268] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing.

[0269] This oxidative dying process is also applicable if it is dividedin two steps:

[0270] step 1: prefixing with peroxide, and then the removal of rollers

[0271] step 2: after fixing with dying.

EXAMPLE 18

[0272] The ready-to-use dye compositions below are prepared (contents ingrams): Compositions 1(N) 2(N) 3(N) 4(N) Hydroxyethylcellulose 1.0 A.M.sold under the name NATROSOL 250 HHR by the company AQUALONCarboxymethylcellulose 1.0 A.M. sold under the name BLANOSE 7M by thecompany AQUALON Resin of guar sold under 1.0 A.M. the name VIDOGUM GH175by the company UNIPECTINE Resin of scleroglucane 1.0 A.M. sold under thename AMIGEL by the company ALBAN MULLER INTERNATINAL Ethanol 10 10 10 102-Amine-2-methyl-1- pH 9 pH 9 pH 9 pH 9 propanol Cationic dye of 0.2 0.20.2 0.2 formula (I) of example 1 Demineralized water qs 100 100 100 100

[0273] Each of the ready-to-use dye compositions are applied for 30minutes to locks of natural grey hair containing 90% white hairs. Thehair is then rinsed, washed with a standard shampoo and then dried.

[0274] The locks of hair are dyed in brilliant red-tinged violet shade.

[0275] Compositions 5(N)″ to 19(N)″ are identical to compositions 1(N)to 4(N), with the proviso that 2-amino-2-methyl-1-propanol is replacedby a basifying agent N′. compositions basifying agent N′  5(N)^(II)potassium carbonate  6(N)^(II) sodium carbonate  7(N)^(II)triethanolamine  8(N)^(II) diethanolamine  9(N)^(II) monoethanolamine10(N)^(II) sodium hydroxide 11(N)^(II) potassium hydroxide 12(N)^(II)N,N-dimethyl-N′-ethylenediamine 13(N)^(II) 4-(ethylamino)-b-butylamine14(N)^(II) N-(n-propyl)-1,3-propanediamine 15(N)^(II)N,N-diethylenediamine 16(N)^(II) N,N,N′,N′-Tetramethylethylenediamine17(N)^(II) N,N-dimethylhydrazine 18(N)^(II) 2-n-butylaminmoethylamine19(N)^(II) 1,6-diaminohexane

[0276] Composition 20(N)′ is identical to compositions 1 (N) and 5(N)″to 1 9(N)″, with the proviso that hydroxyethylcellulose is replaced by ahydroxypropylcellulose.

EXAMPLE 19

[0277] Permanent wave composition consisting of two compositions O,1(O)-5(O), and P, 1(P)-5(P).

[0278] Compositions O and P are prepared according to common processes.% by weight Composition 1(O) Cationic dye of formula (I) 0.2 35-volumeshydrogen peroxide solution 4.3 Cetanol 0.5 Hydrated lanoline 0.35Actealdehyde 0.02 Sodiumpyrophphate 0.025 Phosphoric acid, purifiedwater(with phosphoric 100 acid adjusted to pH 6.5 Composition 1(P)Ammoniumthioglycolate solution (50% by volumes 13.6 thioglycolic acid)Ammoniumcicarbonate 3.5 Disodiumedetat 0.1 Monoethanolamine, purifiedwater(with monoethanolamine 100 adjusted to pH 6.5)

[0279] Process:

[0280] According to common processes, white hair, which tips are wrappedup in paper, is rolled up on a stick of synthetic material (stick with1.5 cm in diameter). This stick is then dipped in the composition 1 (P)for 15 minutes at 30° C., and afterwards rinsed with water for 1 minute.Then the stick is dipped in the composition O1 for 15 minutes at 30° C.and afterwards rinsed with water, washed with a standard shampoo andthen dried. In this way the white hair is homogeneously dyed and wavedfrom the roots up to the tips. % by weight Composition 2(O) Cationic dyeof formula (I) of example 1 0.2 Potassiumbromate 10.2Lauryldimethylacetic acid betain 1.0 Cetyltrimethylammoniumchloride 0.6Sodiumbenzoate 0.3 Salicylacid 0.05 Trisodiumphosphate 0.27 Phosphoricacid, purified water(with phosphoric acid 100 adjusted to pH 6.5Composition 2(P) L-Cysteine hydrochloride 7.0 Cetanol 0.5 Oleylalcohol0.5 Polyoxyethylenethter (10 UO) 1.0 Polyoxyetheylencetylether (15 UO)1.0 Sodiumedetat 0.1 Monoethanolamine, purified water (withmonoethanolamine 100 adjusted to pH 9)

[0281] White hair is treated in the same way as given above in theprocess of example 9 with the proviso that 1 (P) is replaced by 2(P) and1(O) is replaced by 2(O). % by weight Composition 3(O) Cationic dye offormula (I) of example 1 0.2 Uricase (20 U/mg) 1.0 Uric acid 1.0Glycerine 3.0 Purified water qs 100 Composition 3(P)Ammoniumthioglycolate solution (50% by volumes 7.0 thioglycolic acid)Polyoxyethylenether (10 UO) 1.0 Polyoxyetheylencetylether (15 UO) 1.0Sodiumlaurylsulphate 0.5 Collagen hydrolysate solution 0.4Disodiumedetat 0.1 Ammonia water, purified water(with Ammonia water, 100adjusted to pH 9)

[0282] White hair is treated in the same way as given above in theprocess of example 9 with the proviso that 1 (P) is replaced by 3(P) and1(O) is replaced by 3(O). % by weight Composition 4(O) Cationic dye offormula (I) of example 1 0.4 Monoethanolamine, purified water (withmonoethanolamine 100 adjusted to pH 8) Composition 4(P)/oxiative fixingformulation Sodiumbromate 17.0 Lauryldimethylaceticacidbetain 1.5Cetyltrimethylammoniachloride 1.0 Sodiumbenzoate 0.6 Salicylicacid 0.1Trisodiumphophate 0.54 Phosphoric acid, purified water(with phosphoricacid 100 adjusted to pH 6.5

[0283] White hair is treated in the same way as given above in theprocess of example 9 with the proviso that 1 (P) is replaced by 3(P) and1(O) is replaced by a mixture of the two compositions 4(O) and 4(P) in aratio of 1:1. % by weight Composition 5(O) Cationic dye of formula (I)of example 1 0.2 % by weight in relation to the composition P5Composition 5(P)/oxidative fixing formulation Sodiumbromate 8.5Lauryldimethylaceticacidbetain 1.0 Cetyltrimethylammoniachloride 0.6Sodiumbenzoate 0.3 Salicylicacid 0.05 Trisodiumphophate 0.27 Phosphoricacid, purified water(with phosphoric acid 100 adjusted to pH 6.5

[0284] White hair is treated in the same way as given above in theprocess of example 9 with the proviso that 1 (P) is replaced by 3(P) and1(O) is replaced by a mixture of the two compositions 5(O) and 5(P) in aratio of 1:10. Composition 6(O) % by weight Cationic dye of formula (I)of example 1 0.2 Hydroxyethylcellulose 2.5 Triethanolamine, purifiedwater(with triethanolamine 100 adjusted to pH 8.0) qs

[0285] White hair which is treated with the above cited compositions ishomogeneously waved and dyed in a brilliant red-tinged violet shade.

EXAMPLE 20

[0286] The ready-to-use dye compositions below are prepared (contents ingrams): Compositions 1(Q) 2(Q) 3(Q) 4(Q) 5(Q) Cationic dye of 0.2 0.20.15 0.12 0.1 formula (I) of example 1 Cocoglutamate of 5.0 A.M.triethanolamine sold under the name ACYGLUTAMATE CT12 by the companyAJINOMOTO Laurylsarcorsinate 5.0 A.M. of sodium sold under the nameORAMIX L30 by the company SEPPIC Cocoylicethionate of 5.0 A.M. sodiumsold under the name JORDAPON POWDER by the company PPG Laurylether 5.0A.M. carboxilic acid (10 UO) sold under the name AKYPO RLM 100 by thecompany KAO Sodium salt of 5.0 A.M. Tartaric ester ofcocoylpolyglycoside sold under the name GUCAROL AGE ET by the companyCESALPINE Ethanol 10 10 10 10 10 2-Amine-2-methyl- pH 9 pH 9 pH 9 pH 9pH 9 1-propanol qs Demineralized 100 100 100 100 100 water qsq

[0287] The resulting compositions are applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The hair is then rinsed,washed with a standard shampoo and then dried.

[0288] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing.

[0289] Compositions 6(Q)″ to 20(Q)″ are identical to compositions 1 (Q)to 5(Q), with the proviso that 2-amino-2-methyl-1-propanol is replacedby a basifying agent Q′. compositions basifying agent Q′  6(Q)^(II)potassium carbonate  7(Q)^(II) sodium carbonate  8(Q)^(II)triethanolamine  9(Q)^(II) diethanolamine 10(Q)^(II) monoethanolamine11(Q)^(II) sodium hydroxide 12(Q)^(II) potassium hydroxide 13(Q)^(II)N,N-dimethyl-N′-ethylenediamine 14(Q)^(II) 4-(ethylamino)-b-butylamine15(Q)^(II) N-(n-propyl)-1,3-propanediamine 16(Q)^(II)N,N-diethylenediamine 17(Q)^(II) N,N,N′,N′-Tetramethylethylenediamine18(Q)^(II) N,N-dimethylhydrazine 19(Q)^(II) 2-n-butylaminmoethylamine20(Q)^(II) 1,6-diaminohexane

[0290] Composition 21 (Q)′ is identical to compositions (Q) and (Q)″,with the proviso that ethanol is replaced by a isopropanol.

EXAMPLE 21

[0291] The ready-to-use dye compositions below are prepared (contents ingrams): Compositions 1(R) 2(R) 3(R) 4(R) 5(R) 6(R) 7(R) 8(R) Cationicdye 0.12 0.1 0.11 0.12 0.20 0.10 0.20 0.15 of formula (I) of example 1Alkylpoly- 8.0 8.0 glucoside sold under the name ORAMIX CG110 by thecompany SEPPIC N-Decanonyl- 8.0 8.0 N-methyl- glucamine** O-Hexa- 8.08.0 decanoyl-6- αD-glucose N-Cocolacto- 8.0 8.0 bionamide Ethanol 10 1010 10 10 10 10 10 2-Amine-2- pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 pH 9methyl-1- propanol qs Demineralized 100 100 100 100 100 100 100 100water qsq

[0292] The resulting compositions are applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The hair is then rinsed,washed with a standard shampoo and then dried.

[0293] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing.

[0294] Compositions 10(R)′ to 24(R)′ are identical to compositions 1(R)to 8(R), with the proviso that 2-amino-2-methyl-1-propanol is replacedby a basifying agent R′. compositions basifying agent R′ 10(R)^(I)potassium carbonate 11(R)^(I) sodium carbonate 12(R)^(I) triethanolamine13(R)^(I) diethanolamine 14(R)^(I) monoethanolamine 15(R)^(I) sodiumhydroxide 16(R)^(I) potassium hydroxide 17(R)^(I)N,N-dimethyl-N′-ethylenediamine 18(R)^(I) 4-(ethylamino)-b-butylamine19(R)^(I) N-(n-propyl)-1,3-propanediamine 20(R)^(I′)N,N-diethylenediamine 21(R)^(I′) N,N,N′,N′-Tetramethylethylenediamine22(R)^(I′) N,N-dimethylhydrazine 23(R)^(I′) 2-n-butylaminmoethylamine24(R)^(I′) 1,6-diaminohexane

[0295] Compositions 26(R)^(II) to 39(R)^(II) are identical tocompositions 1 (R) to 8(R), with the proviso that alkylpolyglucoside isreplaced by a compound R^(II). compositions compound R^(II) 26(R)^(II)APG 300* 27(R)^(II) APG 350* 28(R)^(II) APG 500* 29(R)^(II) APG 550*30(R)^(II) APG 625* 31(R)^(II) APG base 10-12* 32(R)^(II) ORAMIX CG110** 33(R)^(II) ORAMIX NS 10** 34(R)^(II) LUTENSOL GD 70 sold by compnyBASF 35(R)^(II) PLANTAREN 1200*** 36(R)^(II) PLANTAREN 1300***37(R)^(II) PLANTAREN 2000*** 38(R)^(II) PLANTACARE 818*** 39(R)^(II)PLANTACARE 1200***

[0296] Compositions 40 (R)^(III) to 52(R)^(III) are identical tocompositions (R ), (R)^(I) and (R)^(II) with the proviso thatO-hexadecanoyl-6-αD-glucose is replaced by a compound R^(III).compositions compound R^(III) 40(R)^(III) O-Octanoyl-6-D-glucose41(R)^(III) O-Oleyl-6-D-glucose 42(R)^(III) O-Linoleyl-6-D-glucose43(R)^(III) monostearate methylglucoside 44(R)^(III) sesquistearatemethylglucoside 45(R)^(III) decanoate ethyl-6-glucoside 46(R)^(III) monoand dicocoate(82/7) ethyl-6-glucoside sold under the name BIOSURF COCOby the company NOVO 47(R)^(III) mono and dilaurate (84/8)ethyl-6-glucoside sold under the name BIOSURF 12 by the company NOVO48(R)^(III) monococoate butylglucoside polyoxyethylene with 3 moloxygen/ethylen sold under the name REWOPOL V3122 by the company REWO49(R)^(III) monococoate butylglucoside sold under the name REWOPOL V3101by the company NOVO REWOSAN V 3101 by the company NOVO 50(R)^(III)monococoate butylglucoside sold under the name REWOSAN V 3101 by thecompany NOVO 51(R)^(III) monolaurate of saccharose 52(R)^(III)monococoate of saccharose

[0297] Composition 25(R)′ is identical to any of a composition (R) (R)″and (R)′″, with the proviso that ethanol is replaced by a isopropanol.

EXAMPLE 22

[0298] The dye compositions below are prepared (contents in grams):Compositions 1(S) 2(S) Cationic dye of formula (I) of example 1 0.2 0.2Propylene gylcol 10.0 2-Amine-2-methyl-1-propanol qs pH 9 Demineralizedwater qsq 100 100 Monomethylether of propylene glycol 10.0

[0299] The resulting compositions 1 or 2 are applied for 30 minutes tolocks of natural grey hair containing 90% white hairs. The hair is thenrinsed, washed with a standard shampoo and then dried.

[0300] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing.

[0301] Compositions 3(S)^(I) to 17(S)^(I) are identical to compositions1(S), with the proviso that propylene glycol is replaced by a compoundS′. compositions compound S′  3(S)^(I) glycerine  4(S)^(I)1,3-propanediol  5(S)^(I) 2-butene-1,4-diol  6(S)^(I) pentane-1,5-diol 7(S)^(I) 2,2-dimethyl-propane-1,3-diol  8(S)^(I)3-methyl-pentane-1,5-diol  9(S)^(I) potassium hydroxide 10(S)^(I)pentane-1,2-diol 11(S)^(I) 2,2,4-trimethyl-pentane-1,3-diol 12(S)^(I)2-methylpropane-1,3-diol 13(S)^(I) hexyleneglycol 14(S)^(I)1,3-butyleneglycol 15(S)^(I) dipropyleneglycol 16(S)^(I) diethylenglcol17(S)^(I) triethylenglycol

[0302] Compositions 18(S)^(II) to 29(S)^(II) are identical tocompositions 2(S), with the proviso that monomethylether of propyleneglycol is replaced by a compound S^(II). compositions compound S^(II)18(S)^(II) monoethylether of propylene glycol 19(S)^(II) dimethyletherof isopropylene glycol 20(S)^(II) monomethylether of diethylen glycol21(S)^(II) monomethylether of dipropylen glycol 22(S)^(II)monomethylether of tripropylen glycol 23(S)^(II) monomethylether ofdimethylen glycol 24(S)^(II) monomethylether of diethylen glycol25(S)^(II) monophenylether of ethylen glycol 26(S)^(II) monobenyletherof ethylen glycol 27(S)^(II) monophenylether of propylene glycol28(S)^(II) monophenylether of diethylen glycol 29(S)^(II) monobenyletherof diethylen glycol

[0303] Compositions 30 (S)^(III) to 44(S)^(III) are identical tocompositions 1(S), (S)^(I) and (S)^(II), with the proviso that2-amino-2-methyl-1-propanol is replaced by a basifying agent S^(III).compositions basifying agent S^(III) 30(S)^(III) pottassium carbonate31(S)^(III) sodium carbonate 33(S)^(III) triethanolamine 34(S)^(III)diethanolamnie 35(S)^(III) monoethanolamine 36(S)^(III) sodium hydroxide37(S)^(III) potassium hydroxide 38(S)^(III)N,N-dimethyl-N′-ethylenediamine 39(S)^(III) 4-(ethylamino)-b-butylamine40(S)^(III) N-(n-propyl)-1,3-propanediamine 41(S)^(III)N,N-diethylenediamine 42(S)^(III) N,N,N′,N′-tetramethylethylenediamine43(S)^(III) N,N-dimethylhydrazine 44(S)^(III) 2-n-butylaminmoethylamine45(S)^(III) 1,6-diaminohexane

EXAMPLE 23

[0304] The ready-to-use dye compositions below are prepared (contents ingrams): Compositions 1(T) 2(T) 3(T) Monobromohydrate of 5,6- 0.7dihydroxy indoline 5,6-dihydroxy indole 0.5 1,2,4-Trihydroxy benzene 1.2Cationic dye of formula (I) of 0.1 0.07 0.05 example 1 Common dyesupport (*) (*) (*) (*) Demineralized water q.s.q 100 100 100 (*) Commondye support: Ethanol 20.0 g Nonylphenoloxyethylen with 9 mol oxyethylen 8.0 g sold under the name IGEPAL NR 9 Or by the company RHODIA CHEMIE2-Amino-2-methyl-1-propanol qs. pH = 8.0

[0305] Each of the ready-to-use dye compositions are applied for 30minutes to locks of natural grey hair containing 90% white hairs. Thehair is then rinsed, washed with a standard shampoo and then dried.

[0306] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing.

[0307] Compositions 4(T)^(I) to 9(T)^(I) are identical to compositions3(T), with the proviso that 1,2,4-trihydroxy benzene is replaced by acompound T^(II). Compositions compound T′ 4(T)^(I)1-methyl-2,4,5-trihydroxy benzene 5(T)^(I) 2,4-diamino-6-methyl phenol6(T)^(I) 2-amino-4-methylamino phenol 7(T)^(I) 2,4-diamino-4-methylphenol 8(T)^(I) 2,6-diamino-4-diethylamino phenol 9(T)^(I)2,6-diamino-1,4-dihydroxy benzene

[0308] Compositions 10(T)^(II) to 17(T)^(II) are identical tocompositions 2(T), with the proviso that 5.6-dihydroxy indole isreplaced by a compound T^(II). compositions compound T^(II) 10(T)^(II′)2-methyl-5,6-dihydroxy indole 11(T)^(II) 3-methyl-5,6-dihydroxy indole12(T)^(II′) 1-methyl-5,6-dihydroxy indole 13(T)^(II)2,3-dimethyl-5,6-dihydroxy indole 14(T)^(II) 5-methoxy-6-hydroxy indole15(T)^(II′) 5-acetoxy-6-hydroxy indole 16(T)^(II) 5,6-diacetoxy indole17(T)^(II′) 5,6-dihydroxy indole carbonic acid

[0309] Compositions 18(T)^(III) to 20(T)^(III) are identical tocompositions 1(T), with the proviso that monobromohydrate of5,6dihydroxy indoline is replaced by a compound T^(III). compositionscompound T^(III) 18(T)^(III′) 5,6-dihydroxy indoline 19(T)^(III)1-methyl-5,6-dihydroxy indoline 20(T)^(III′) 1-ethyl-5,6-dihydroxyindoline

EXAMPLE 24

[0310] Dying compositions possessing pH 9.8 are prepared by mixingidentical percentages of weight of a hydrogen peroxide solution (6% byweight) and a oxidative precursor dye composition prepared as givenbelow in table 1: TABLE 1 Oxidative precursor dye composition(contentsin percentage by weight) Oxidative dye compositions 1(V) 2(V) 3(V) 4(V)2,5,6-Triamino-4-hydroxypyrimidine 0.01 0.2 0.2 0.01 sulphate4-Amino-2-hydroxytoluene 0.5 0.5 2,5-Diaminotoluene sulphate 0.55 0.70.7 0.55 *common dye support 4-Chlororesorcine 0.17 0.17 Resorcine 0.050.05 Ascorbic acid 0.5 0.5 Cationic dye * in % by weight 1.0 1.03-Aminophenol 0.03 0.03 Demineralized water qs. 100 100 100 100 for forfor for *common dye support 1(V) 2(V) 3(V) 4(V) Cetylstearylalcohol11.00 11.00 Oleth-5 5.0 5.00 Oleic acid 2.5 10.0 10.0 2.50 Stearic acidmonoethanolamide 2.5 2.50 Coco fatty acid monoethanolamide 2.5 2.5Sodium laurylsuphate 1.7 1.7 Sodiumsulphite 1.0 1.00 1.00 1.001,2-Propanediol 1.0 1.00 Ammoniumchloride 0.5 0.50 EDTA, Tetrasodiumsalt0.2 0.20 Perfume 0.4 0.40 Cornproteinhydrolysate 0.2 0.20 Silica 0.10.10 compositions (V^(I)) = compositions (V^(I))′ = composition 4(V) +composition 3(V) + *Cationic dye *cationic dye *cationic dye Cationicdye of example 1 10(V^(I)) 10(V^(I))′ Cationic dye of example 211(V^(I)) 11(V^(I))′ Cationic dye of example 3 12(V^(I)) 12(V^(I))′Cationic dye of example 4 13(V^(I)) 13(V^(I))′ compositions (V^(I)) =composition 4(V) + *cationic dye + dye** (*cationic dye/**dye in a ratioof 1:1) cationic dye cationic dye cationic dye cationic dye of dye** ofexample 1 of example 2 of example 3 example 4 HC Yellow 2  14(V^(I)) 15(V^(I))  16(V^(I))  17(V^(I)) HC Yellow 4  18(V^(I))  19(V^(I)) 20(V^(I))  21(V^(I)) HC Yellow 6  22(V^(I))  23(V^(I))  24(V^(I)) 25(V^(I)) Basic Yellow  57 26(V^(I))  27(V^(I))  28(V^(I))  29(V^(I))Basic Yellow 9  30(V^(I))  31(V^(I))  32(V^(I))  33(V^(I)) DisperseOrange 3  34(V^(I))  35(V^(I))  36(V^(I))  37(V^(I)) HC Red 3  38(V^(I)) 9(V^(I))  40(V^(I))  41(V^(I)) HC Red BN  42(V^(I))  43(V^(I)) 44(V^(I))  45(V^(I)) Basic Red 76  46(V^(I))  47(V^(I))  48(V^(I)) 49(V^(I)) Basic Red 2  50(V^(I))  51(V^(I))  52(V^(I))  53(V^(I)) BasicViolet 14  54(V^(I))  55(V^(I))  56(V^(I))  57(V^(I)) Basic Blue 3 58(V^(I))  59(V^(I))  60(V^(I))  61(V^(I)) Basic Blue 6  62(V^(I)) 63(V^(I))  64(V^(I))  65(V^(I)) Basic Blue 7  66(V^(I))  67(V^(I)) 68(V^(I))  69(V^(I)) Basic Blue 9  70(V^(I))  71(V^(I))  72(V^(I)) 73(V^(I)) Basic Blue 12  74(V^(I))  75(V^(I))  76(V^(I))  77(V^(I))Basic Blue 26  78(V^(I))  79(V^(I))  80(V^(I))  81(V^(I)) HC Blue 2 82(V^(I))  83(V^(I))  84(V^(I))  85(V^(I)) HC Blue 7  86(V^(I)) 87(V^(I))  88(V^(I))  89(V^(I)) HC Blue 12  90(V^(I))  91(V^(I)) 92(V^(I))  93(V^(I)) Disperse Blue 3  94(V^(I))  95(V^(I))  96(V^(I)) 97(V^(I)) HC Violet 1  98(V^(I))  99(V^(I)) 100(V^(I)) 101(V^(I))Disperse Violet 1 102(V^(I)) 103(V^(I)) 104(V^(I)) 105(V^(I)) DisperseBlack 9 106(V^(I)) 107(V^(I)) 108(V^(I)) 109(V^(I)) Basic Brown 16110(V^(I)) 111(V^(I)) 112(V^(I)) 113(V^(I)) Basic Brown 17 114(V^(I))115(V^(I)) 116(V^(I)) 117(V^(I)) 2-amino-6-chloro-4-nitrophenol118(V^(I)) 119(V^(I)) 120(V^(I)) 121(V^(I))4-amino-2-nitrodiphenylamine-2′-carboxylic acid 122(V^(I)) 123(V^(I))124(V^(I)) 125(V^(I)) 6-nitro-1,2,3,4-tetrahydroquinoxaline 126(V^(I))127(V^(I)) 128(V^(I)) 129(V^(I))4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene 130(V^(I))131(V^(I)) 132(V^(I)) 133(V^(I)) hydrochloride1-methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene 135(V^(I)) 136(V^(I))137(V^(I)) 138(V^(I)) compositions (V^(I)) = composition 4(V) +*cationic dye + dye*** (*cationic dye/***dye in a ratio of 1:1) cationicdye cationic dye cationic dye of cationic dye dyes*** of example 1 ofexample 2 example 3 of example 4 HC Yellow 2, HC Yellow 4 139(V^(I))140(V^(I)) 141(V^(I)) 142(V^(I)) Basic Red 76, HC Red BN, 143(V^(I))144(V^(I)) 145(V^(I)) 146(V^(I)) HC Red BN, Basic Violet 14 147(V^(I))148(V^(I)) 149(V^(I)) 150(V^(I)) Basic Blue 12, Basic Blue 6 151(V^(I))152(V^(I)) 153(V^(I)) 154(V^(I))4-N-ethyl-1,4-bis(2′-hydroxyethylamino)-2-nitrobenzene 155(V^(I))156(V^(I)) 157(V^(I)) 158(V^(I)) hydrochloride,6-nitro-1,2,3,4-tetrahydroquinoxaline Basic Brown 16, Disperse Black 9159(V^(I)) 160(V^(I)) 162(V^(I)) 163(V^(I)) compositions (V^(I)) =composition 4(V) + *cationic dye + dye**** (*cationic dye/****dye in aratio of 1:1) cationic dye cationic dye cationic dye of cationic dye ofdyes**** of example 1 of example 2 example 3 example 4 HC Yellow 2, HCYellow 4, Basic Red 2 164(V^(I)) 165(V^(I)) 166(V^(I)) 167(V^(I)) BasicRed 76, HC Red BN, Basic Red 2 168(V^(I)) 169(V^(I)) 170(V^(I))171(V^(I)) HC Red BN, Basic Violet 14, Disperse Violet 1 172(V^(I))173(V^(I)) 174(V^(I)) 175(V^(I)) Basic Blue 12, Basic Blue 6, DisperseViolet 1 176(V^(I)) 177(V^(I)) 178(V^(I)) 179(V^(I))2-amino-6-chloro-4-nitrophenol, 6-nitro- 180(V^(I)) 181(V^(I))182(V^(I)) 183(V^(I)) 1,2,3,4-tetrahydroquinoxaline, Basic Brown 17Basic Brown 16, Disperse Black 9, Basic Brown 17 184(V^(I)) 185(V^(I))186(V^(I)) 187(V^(I)) compositions (V^(I)) = composition 4(V) +*cationic dye + dye***** (*cationic dye/*****dye in a ratio of 1:1)cationic dye cationic dye cationic dye cationic dye dye***** of example1 of example 2 of example 3 of example 4 HC Yellow 2, Basic Red 76,Basic Red 2, Disperse Orange 3 188(V^(I)) 189(V^(I)) 190(V^(I))191(V^(I)) Basic Red 76, HC Red BN, Basic Red 2, Basic Violet 14192(V^(I)) 193(V^(I)) 194(V^(I)) 195(V^(I)) HC Red BN, Basic Violet 14,Disperse Violet 1, HC Red 3 196(V^(I)) 197(V^(I)) 197(V^(I)) 198(V^(I))Basic Blue 12, Basic Blue 6, Disperse Violet 1, Basic Blue 9 199(V^(I))200(V^(I)) 201(V^(I)) 202(V^(I)) 2-amino-6-chloro-4-nitrophenol,6-nitro- 203(V^(I)) 204(V^(I)) 205(V^(I)) 206(V^(I))1,2,3,4-tetrahydroquinoxaline, Basic Brown 17, HC Red BN Basic Brown 16,Disperse Black 9, Basic Brown 17, Basic Red 207(V^(I)) 208(V^(I))209(V^(I)) 210(V^(I)) 76

[0311] Each of the oxidative precursor dye compositions 1 (V), 2(V),3(V) and 4(V) are applied for 15 minutes to locks of bleached hair. Thehair is then not rinsed, but treated for 15 minutes with a oxidativeprecursor dye compositions(V^(II)) which is prepared as given in table 2below: TABLE 2 oxidative precursor dye compositions(V^(II)) oxidativeprecursor dye composition 1(V) and 1(V^(II)) a cationic dye of example 1as solution (1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidativeprecursor dye composition 1(V) and 2(V^(II)) a cationic dye of example 2as solution (1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidativeprecursor dye composition 1(V) and 3(V^(II)) a cationic dye of example 3as solution (1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidativeprecursor dye composition 1(V) and 4(V^(II)) a cationic dye of example 4as solution (1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidativeprecursor dye composition 1(V) and a 4/14(V^(II)) to cationic dyecomposition 14(V^(I))-210(V^(I)) as solution (1.0% by weight) with4/210(V^(II)) pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 5(V^(II)) a cationic dye of example 1 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 6(V^(II)) a cationic dye of example 2 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 7(V^(II)) a cationic dye of example 3 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 8(V^(II)) a cationic dye of example 4 as solution(1.0% by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 8/14(V^(II)) to a cationic dye composition14(V^(I))-210(V^(I)) as solution (1.0% by weight) with 8/210(V^(II)) pH9.8; in a ratio of 1:1 oxidative precursor dye composition 1(V) and11(V^(II)) a cationic dye of example 1 as solution (1.0% by weight) withpH 5 (adjusted with citric acid); in a ratio of 1:1 oxidative precursordye composition 1(V) and 12(V^(II)) a cationic dye of example 2 assolution (1.0% by weight) with pH 5 (adjusted with citric acid); in aratio of 1:1 oxidative precursor dye composition 1(V) and 13(V^(II)) acationic dye of example 3 as solution (1.0% by weight) with pH 5(adjusted with citric acid); in a ratio of 1:1 oxidative precursor dyecomposition 1(V) and 14(V^(II)) a cationic dye of example 4 as solution(1.0% by weight) with pH 5 (adjusted with citric acid); in a ratio of1:1 oxidative precursor dye composition 1(V) and 14/14(V^(II)) to acationic dye composition 14(V^(I))-210(V^(I)) solution (1.0% by weight)with 14/210(V^(II)) pH 5 (adjusted with citric acid); in a ratio of 1:1oxidative precursor dye composition 2(V) and 15(V^(II)) a cationic dyeof example 1 as solution (1.0% by weight) with pH 5 (adjusted withcitric acid); in a ratio of 1:1 oxidative precursor dye composition 2(V)and 16(V^(II)) a cationic dye of example 2 as solution (1.0% by weight)with pH 5 (adjusted with citric acid); in a ratio of 1:1 oxidativeprecursor dye composition 2(V) and 17(V^(II)) a cationic dye of example3 as solution (1.0% by weight) with pH 5 (adjusted with citric acid); ina ratio of 1:1 oxidative precursor dye composition 2(V) and 18(V^(II)) acationic dye of example 4 as solution (1.0% by weight) with pH 5(adjusted with citric acid); in a ratio of 1:1 oxidative precursor dyecomposition 2(V) and 18/14(V^(II)) to a cationic dye composition14(V^(I))-210(V^(I)) as solution (1.0% by weight) with 18/210(V^(II)) pH5 (adjusted with citric acid); in a ratio of 1:1 oxidative precursor dyecomposition 3(V) with pH 5 (adjusted with citric acid) 19(V^(II))oxidative precursor dye composition 4(V) with pH 5 (adjusted with citricacid) 20(V^(II)) oxidative precursor dye composition 3(V) comprisingcationic dye composition 14(V^(I))-210(V^(I)) 20/14(V^(II)) to with pH 5(adjusted with citric acid) 20/210(V^(II)) oxidative precursor dyecomposition 4(V) comprising cationic dye composition14(V^(I))-210(V^(I)) 21/14(V^(II)) to with pH 5 (adjusted with citricacid) 21/210(V^(II)) cationic dye of example 1 in a watery citric gel(12.5% by weight) with pH 5; 22(V^(II)) in an equimolar weight portionto the weight of composition 3(V) cationic dye of example 2 in a waterycitric gel (12.5% by weight) with pH 5; 23(V^(II)) in an equimolarweight portion to the weight of composition 3(V) cationic dye of example3 in a watery citric gel (12.5% by weight) with pH 5; 24(V^(II)) in anequimolar weight portion to the weight of composition 3(V) cationic dyeof example 4 in a watery citric gel (12.5% by weight) with pH 5;25(V^(II)) in an equimolar weight portion to the weight of composition3(V) cationic dye composition 14(V^(I))-210(V^(I)) a watery citric gel(12.5% by weight) with pH 5; 25/14(V^(II)) to in an equimolar weightportion to the weight of composition 3(V) 25/210(V^(II)) cationic dye ofexample 1 as solution (1.0% by weight) with pH 9.8; 26(V^(II)) in anequimolar weight portion to composition 3(V) cationic dye of example 2as solution (1.0% by weight) with pH 9.8; 27(V^(II)) in an equimolarweight portion to composition 3(V) cationic dye of example 3 as solution(1.0% by weight) with pH 9.8; 28(V^(II)) in an equimolar weight portionto composition 3(V) cationic dye of example 4 as solution (1.0% byweight) with pH 9.8; 29(V^(II)) in an equimolar weight portion tocomposition 3(V) cationic dye composition 14(V^(I))-210(V^(I)) assolution (1.0% by weight) with pH 9.8; 29/14(V^(II)) to in an equimolarweight portion to composition 3(V) 29/210(V^(II))

[0312] Each of the oxidative precursor dye compositions 3(V) and 4(V)are applied for 15 minutes to locks of bleached hair. The hair is thennot rinsed, but treated for 15 minutes with a oxidative precursor dyecompositions(V^(II)) which is prepared as given in table 3 below: TABLE3 oxidative precursor dye compositions(V^(II)) oxidative precursor dyecomposition 2(V) with pH 9.8;  9(V^(II)) in a ratio of 1:1 oxidativeprecursor dye composition 1(V) with pH 9.8; 10(V^(II)) in a ratio of 1:1

[0313] Then the hair is rinsed, washed with a standard shampoo andafterwards dried.

[0314] The hair is dyed in a brilliant shades with very good enduranceproperties with respect to subsequent shampooing and fastness to rubbingand lightness.

EXAMPLE 25

[0315] Example 25 is identical to example 24 with the proviso that thedying compositions do not possess pH 9.8, but pH 5 (pH value is adjustedwith citric acid)

EXAMPLE 26

[0316] Example 26 is identical to example 24 with the proviso that theoxidative precursor dye compositions (V^(II)) are replaced by theoxidative precursor dye compositions (W^(II)) which are prepared asgiven in table 1 below. TABLE 1 dye compositions (W^(II)) Oxidativeprecursor dye compositions 1(W^(I)) and hydrogen  1(W^(II)) peroxidesolution (6% by weight); with pH 5 (adjusted with citric acid); in aratio of 1:1 Oxidative precursor dye compositions 2(W^(II)) and hydrogen 2(W^(II)) peroxide solution (6% by weight); with pH 9.8; in a ratio of1:1 Oxidative precursor dye compositions 1(W^(II)) and hydrogen 3(W^(II)) peroxide solution (6% by weight); with pH 9.8; in a ratio of1:1 Oxidative precursor dye compositions 2(W^(II)) and hydrogen 4(W^(II)) peroxide solution (6% by weight); with pH 5; in a ratio of1:1 Cationic dye of example 1 (1.0% by weight) in a watery citric 5(W^(II)) gel (12.5% by weight) with pH 5; in a ratio of weight of 1:1to composition 3(W^(I)) Cationic dye of example 2 (1.0% by weight) in awatery citric  6(W^(II)) gel (12.5% by weight) with pH 5; in a ratio ofweight of 1:1 to composition 3(W^(I)) Dye of example 4 with pH 9.8; in aratio of weight of 1:1 to  7(W^(II)) composition 3(W^(I)) Dye of example4) with pH 9.8 and hydrogen peroxide  8(W^(II)) solution (6% by weight);in a ratio of weight of 1:1 to composition 3(W^(I)) Cationic dye ofexample 3 (1.0% by weight) in a watery citric  9(W^(II)) gel (12.5% byweight) and hydrogen peroxide solution (6% by weight); with pH 5(adjusted with citric acid); in a ratio of 1:1 Cationic dye of example 3(1.0% by weight) in a watery citric 10(W^(II)) gel (12.5% by weight)with pH 5; in a ratio of weight of 1:1 to composition 3(W^(I)) Cationicdye of example 4 (1.0% by weight) in a watery citric 11(W^(II)) gel(12.5% by weight) with pH 5; in a ratio of weight of 1:1 to composition3(W^(I))

[0317] Then the locks of bleached hair is treated till of 7 is adjusted.After 15 minutes at pH 7 the hair is rinsed, washed with a standardshampoo and then dried.

[0318] The hair is dyed in a brilliant red-tinged violet shade with verygood endurance properties with respect to subsequent shampooing andfastness to rubbing and lightness.

EXAMPLE 27

[0319] Example 27 is identical to example 26 with the proviso that theoxidative precursor dye compositions (W^(II)) are applied to the locksof bleached hair by a comb.

EXAMPLE 28

[0320] Example 28 is identical to example 25 with the proviso that theoxidative precursor dye compositions are applied to the locks ofbleached hair by a comb.

EXAMPLES 29-32

[0321] Example 29 is identical to example 24, and

[0322] Example 30 is identical to example 25, and

[0323] Example 31 is identical to example 26, and

[0324] Example 32 is identical to example 27, and

[0325] Example 33 is identical to example 28,

[0326] with the proviso that the dying concerns not “locks of bleachedhair”, but “locks of middle blonde hair”.

EXAMPLES 33-37

[0327] Example 33 is identical to example 24, and

[0328] Example 34 is identical to example 25, and

[0329] Example 35 is identical to example 26, and

[0330] Example 36 is identical to example 27, and

[0331] Example 37 is identical to example 28, with the proviso that thedying concerns not “locks of bleached hair”, but ubleached hair.

EXAMPLES 38-42

[0332] Example 38 is identical to example 24, and

[0333] Example 39 is identical to example 25, and

[0334] Example 40 is identical to example 26, and

[0335] Example 41 is identical to example 27, and

[0336] Example 42 is identical to example 28, with the proviso that thedying concerns not “locks of bleached hair”, but “middle blonde hair”.

[0337] All of the forgoing examples can also be carried out without theuse of a common dye support.

[0338] In all of the forgoing examples the identified common dye supportcan be replaced by the following dye support: (*) Common dye support:Ethanol 20.0 g Poly(C₈—C₁₀)alkylglucoside as an aqueous solution  4.8 gcontaining 60% active material (A.M.) buffered with ammonium citrate(0.5%), sold under the name Oramix CG110 ® by the company SEPPIC pHagent Qs pH = 6.5

[0339] or by

[0340] In all of the forgoing examples the identified common dye supportcan be replaced by the following dye support: Common dye support:Ethanol 20.0 g Nonylphenoloxyethylen with 9 mol oxyethylen  8.0 g soldunder the name IGEPAL NR 9 Or by the company RHODIA CHEMIE2-Amino-2-methyl-1-propanol qs. pH = 8.0

[0341] or by Common dye support: Oleic acid 10.0 Sodiumsulphite 1.00

What is claimed is:
 1. A method of colouring keratin-containing fibresthat comprises treating the fibres with a dye of formula

wherein Y₁ and Y₂ are each independently of the other hydrogen,unsubstituted or substituted C₁-C₄-alkyl, or halogen, R₁ and R₂ are eachindependently of the other hydrogen or unsubstituted or substitutedC₁-C₄alkyl, R₃ and R₄ are each independently of the other hydrogen,unsubstituted or substituted C₁-C₄-alkyl, C₁-C₄alkoxy or halogen, R₅ ishydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or halogen, X is C₁-C₁₂alkoxy or agroup of formula —N(R₆)—CO—R₇, wherein R₆ is hydrogen or C₁-C₄alkyl andR₇ is hydrogen, C₁-C₄alkyl or —NH₂ and A⁻ is an anion.
 2. A method ofcolouring keraun-containing fibres acoording to claim 1 comprising a1)treating the fibres with a composition, possessing a pH value of pH >7,and comprising a developing substance and at least one couplingsubstance and an oxidation agent, or a2)treating the fibres with acomposition, possessing a pH value of pH <7, comprising a developingsubstance and at least one coupling substance and an oxidation agent, ora3) treating the fibres with a dye of formula (1) according to claim 1,or with a dye of formula (4) according to claim 3, or with a compositionaccording to claim 5 and a composition, possessing a pH value of pH >7,and comprising a developing substance and at least one couplingsubstance and an oxidation agent, or a4) treating the fibres with a dyeof formula (1) according to claim 1, or with a dye of formula (4)according to claim 3, or with a composition according to claim 5 and acomposition, possessing a pH value of pH <7, and comprising a developingsubstance and at least one coupling substance and an oxidation agent,and b) then applying without intermediary rinsing for 5 to 30 minutes,and c1)then applying to the treated fibres a composition, possessing apH value of pH <7, and comprising a developing substance and at leastone coupling substance, or c2)then applying to the treated fibres acomposition, possessing a pH value of pH >7, and comprising a developingsubstance and at least one coupling substance, or c3)then applying tothe treated fibres a dye of formula (1) according to claim 1, or a dyeof formula (4) according to claim 3, or a composition according to claim5, and a composition, possessing a pH value of pH <7, and comprising adeveloping substance and at least one coupling substance, or c4)thenapplying to the treated fibres a dye of formula (1) according to claim1, or a dye of formula (4) according to claim 2, or a compositionaccording to claim 4, composition, possessing a pH value of pH >7, andcomprising a developing substance and at least one coupling substance,or c5)then applying to the treated fibres a composition, possessing a pHvalue of pH >7, and comprising a dye of formula (1) according to claim1, or a dye of formula (4) according to claim 3, or a compositionaccording to claim 5, or c6)then applying to the treated fibres acomposition, possessing a pH value of pH <7, and comprising a dye offormula (1) according to claim 1, or a dye of formula (4) according toclaim 3, or a composition according to claim 5, with the proviso thatleast one dye of formula (1) according to claim 1, or a dye of formula(4) according to claim 2, or a composition according to claim 4 isapplied to the hair.
 3. A dye of formula

wherein R₁ and R₂ are each methyl or ethyl, X is unsubstitutedC₁-C₄alkoxy or a radical —NH—CO—R₇, wherein R₇ is hydrogen, methyl,ethyl or —NH₂, and A⁻ is an anion.
 4. A process for the preparation of adye of formula (1), which comprises acylating the free amino group in acompound of formula

wherein Y₁, Y₂, R₁, R₂, R₃, R₄, R₅ and A⁻ are as defined for formula(1), in a manner known per se, or reacting a compound of formula

wherein Y₁, Y₂, R₁, R₂, R₃ and R₄ are as defined for formula (1) and R₈is C₁-C₄alkyl with a p-alkoxy-aniline under reaction conditions knownper se.
 5. A composition for colouring keratin-containing fibres, whichcomprises at least one dye of formula (1) according to claim 1.